US20060128996A1 - Compositions containing Ionic liquids and uses thereof, especially in organic synthesis - Google Patents

Compositions containing Ionic liquids and uses thereof, especially in organic synthesis Download PDF

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US20060128996A1
US20060128996A1 US10/529,361 US52936105A US2006128996A1 US 20060128996 A1 US20060128996 A1 US 20060128996A1 US 52936105 A US52936105 A US 52936105A US 2006128996 A1 US2006128996 A1 US 2006128996A1
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carbon atoms
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Michel Vaultier
Said Gmouth
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Centre National de la Recherche Scientifique CNRS
Universite de Rennes 1
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/02—Addition
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    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
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    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
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    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
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    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4266—Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
    • B01J31/0224—Sulfur-containing compounds comprising sulfonyl groups being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
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    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • the present invention relates to compositions containing ionic liquids, as well as their uses, in particular in organic synthesis.
  • ionic liquids have increasingly been used in organic synthesis and in catalysis as they have a certain number of useful and important physico-chemical properties such as their high thermal stability, their low volatilities and their very low vapor pressures, their low inflammability, their strong solubilization power of the salts as well as of the neutral organic molecules and polymers and finally the possibility of easy recycling.
  • One object of the present invention is to provide a novel use of ionic liquids as novel matrices for organic synthesis in homogeneous phase on soluble support(s).
  • One object of the present invention is to provide novel matrices for the organic synthesis on soluble support(s), which are easily recyclable, liquid in a very broad range of temperature, having a very low vapor pressure and possessing a very strong solubilization power.
  • One object of the present invention is to provide novel matrices for organic synthesis on soluble support(s), said soluble support(s) being dissolved in said matrices.
  • One object of the present invention is to provide novel matrices for organic synthesis on soluble support(s) in place of the resins but without the drawbacks linked to reactions in heterogeneous phase on solid support.
  • One object of the present invention is to provide a novel use of ionic liquids, by conferring resin-type properties on these ionic liquids.
  • the present invention relates to the use of an ionic liquid, as liquid matrix for organic synthesis in homogeneous phase on soluble support, without volatile organic solvent, said ionic liquid being presented in liquid or solid form at ambient temperature, of formula A 1 + X 1 ⁇ , A 1 + representing a cation, functional or non-functional, or a mixture of cations in which either none of the cations is functional or at least one of the cations is functional, and X 1 ⁇ an anion, functional or non-functional, or a mixture of anions in which either none of the anions is functional or at least one of the anions is functional.
  • ionic liquid designates a salt or a mixture of salts the melting point of which is comprised between ⁇ 100° C. and 250° C.
  • liquid matrix designates an ionic liquid capable of solubilizing one or more chemical species such as mineral or organic salts, organic molecules, polymers of natural or synthetic origin.
  • the expression “liquid matrix” therefore designates a solvent constituted by an ionic liquid.
  • These novel solvents are non-volatile and have a very low vapor pressure. They are also polar and have the ability to dissolve functional onium salts which can then serve as soluble supports.
  • soluble support designates a salt dissolved in the ionic liquid matrix carrying one or more functions allowing the catching of molecules and their subsequent functionalization as well as the release at the end of the reaction sequence.
  • organic synthesis in homogeneous phase on soluble support designates the conversion(s) of the chemical function(s) carried by the soluble support without modifying the liquid matrix, followed by a cleavage reaction releasing the sought molecule(s).
  • the expression “functional cation” designates a molecular group which possesses at least one chemical function, part of this group carrying a positive charge.
  • the expression “functional anion” designates a molecular group which possesses at least one chemical function, part of this group carrying a negative charge.
  • non-functional cation designates a molecular group which possesses no chemical function, part of this group carrying a positive charge.
  • non-functional anion designates a molecular group which possesses no chemical function, part of this group carrying a negative charge.
  • the A 1 + X 1 ⁇ matrix comprises no functional ion, it serves as a reaction medium which is inert vis-à-vis reagents but is capable of dissolving them.
  • the A 1 + X 1 ⁇ matrix comprises at least one functional ion, it can serve on the one hand as a reaction medium and on the other hand as a soluble support.
  • the A 1 + X 1 ⁇ matrix can contain several non-functional cations and/or anions for the following reasons:
  • the mixture of cations can originate from industry.
  • numerous detergents based on ammonium or phosphonium cations are mixtures of salts produced as such by synthesis. They correspond to cuts. Thousands of tons are thus produced at a low price. The benefit of using such mixtures within the framework of the present invention is therefore economic.
  • the melting point of a mixture is lower than the melting point of the constituent of the mixture which melts at the lowest temperature. It can therefore be very important to resort to a mixture in order to have an ionic liquid at a reasonable melting temperature.
  • Certain functionalized salts in particular those with large anions such as NTf 2 ⁇ , PF 6 ⁇ , BF 4 ⁇ or CF 3 SO 3 ⁇ , can be liquid at ambient temperature or can melt at low temperature, for example NTf 2 ⁇ is liquid at ambient temperature.
  • This ionic liquid is prepared by alkylation of Me 3 N according to the following reaction:
  • the present invention relates to the use as defined above, characterized in that A 1 + represents a non-functional cation or a mixture of non-functional cations and X 1 ⁇ a non-functional anion or a mixture of non-functional anions.
  • the present invention also relates to the use as defined above, characterized in that:
  • a 1 + represents a functional cation or a mixture of cations at least one of which of is functional
  • X 1 ⁇ represents a functional anion or a mixture of anions at least one of which is functional
  • said functional cations and functional anions corresponding to an ionic entity, namely respectively cationic or anionic, linked to at least one function F i , F i varying from F 0 to F n , n being an integer varying from 1 to 10.
  • the expression “ionic entity” designates the part of the cation or of the anion, which carries the charge, respectively positive or negative.
  • the function F i is in particular chosen from the following functions:
  • the present invention relates to the use of an ionic liquid as defined above, for the preparation of a stable composition containing in solution:
  • the functionalized salt in particular the functionalized onium salt, being dissolved in the liquid matrix, in order to form a homogeneous phase
  • a 1 + representing a non-functional cation or a mixture of cations in which none of the cations is functional
  • X 1 ⁇ representing a non-functional anion or a mixture of anions in which none of the anions is functional
  • a 2+ representing a cation, functional or non-functional, or a mixture of cations in which none of the cations is functional or in which at least one of the cations is functional
  • X 2 ⁇ representing an anion, functional or non-functional, or a mixture of anions in which none of the anions is functional or in which at least one of the anions is functional
  • a 2 + and/or X 2 ⁇ represent(s) or comprise(s) a functional cation and a functional anion respectively,
  • stable composition designates the homogeneous mixture composed of the A 1 + X 1 ⁇ liquid matrix and of the A 2+ X 2 ⁇ functionalized salt(s). This composition is described as stable to the extent that it does not undergo spontaneous conversions over time.
  • composition is stable by spectroscopic analysis using NMR, IR, visible V, of the mass spectrometry or chromatography methods.
  • the expression “functionalized salt (salt with a dedicated task)” designates an entity of type A 2 + X 2 ⁇ in which the cation and/or the anion carries a function F i as previously defined. This function confers chemical and/or physico-chemical properties upon said functionalized salt and upon the stable composition, of which it forms part.
  • the expression “functionalized onium salt” designates ammonium, phosphonium, sulphonium salts, as well as all the salts resulting from the quaternization of an amine, a phosphine, a thioether or a heterocycle containing one or more of these heteroatoms, and carrying at least one function F i .
  • This expression also designates an onium salt the cation of which as defined above is not functionalized but the anion of which carries a function F i .
  • This expression can also designate a salt the anion and the cation of which carry a function F i .
  • a preferred functionalized onium salt is in particular chosen from the following:
  • n being an integer from 0 to 20.
  • a preferred non-functionalized onium salt is in particular chosen from the following: imidazolium, pyridinium Me 3 N + —Bu or Bu 3 P + —Me cations, NTf 2 ⁇ , PF 6 ⁇ or BF 4 ⁇ anions.
  • reaction support designates any salt of A 2 + X 2 ⁇ type functionalized by a function F i which can be converted and cleaved in order to release the sought molecule at the end of the reaction sequence.
  • This expression designates in particular any salt of A 2 + X 2 ⁇ type functionalized by a function F n (last function in the reaction chain) which can be cleaved in order to release the sought molecule at the end of the reaction sequence.
  • L arm designates an alkyl or aralkyl chain which can contain one or more heteroatoms such as nitrogen, phosphorus, sulphur, oxygen, silicon, tin, containing between 1 and 30 carbon atoms, and said arm is in particular chosen from an alkyl chain containing 2 to 10 carbon atoms and 1 to 6 oxygen or nitrogen atoms.
  • the ionic matrix is non-functional and it is necessary that the A 2 + X 2 ⁇ onium salt be functionalized, either via the A 2 + cation, or via the X 2 ⁇ anion, or via the A 2 + cation and the X 2 ⁇ anion.
  • the anion thus obtained can then serve as a reaction intermediate, in particular in Suzuki coupling, according to the following reaction: Bu 4 N + OH ⁇ +Ar 1 B(OH) 2 ⁇ Bu 4 N + Ar 1 ⁇ overscore (B) ⁇ (OH) 3
  • this coupling is “releasing” to the extent that there is no need for a cleavage reaction in order to recover the final product.
  • a functionalized salt involving both the anion and the cation is useful in more complicated sequences. It is possible to selectively modify the cation or the anion and to give rise to the reaction of the anion with the cation in a final conversion via the functions that carry the cation and the anion. It is also possible to start from a functionalized salt only the cation of which is functionalized.
  • the function F 0 is modified in order to obtain the function F i and, by metathesis, a functional anion is introduced the function of which can react with the function F i carried by the functionalized cation.
  • the present invention relates to the use as defined above, for the preparation of a stable composition containing in solution:
  • the abovementioned first novel functions of the second part of said ionic liquid being capable of subsequently being converted into other functions, without affecting one or more initial functions F 0 of the first part of said ionic liquid.
  • the expression “without affecting one or more initial functions F 0 of the first part of said ionic liquid” means that the first novel functions of the second part of said ionic liquid are subsequently converted into other functions, by chemoselective conversions.
  • This particular embodiment of the invention corresponds to the case where the A 1 + X 1 ⁇ ionic liquid plays the role of both liquid matrix and functionalized salt.
  • the A 1 + X 1 ⁇ ionic liquid plays the role of both liquid matrix and functionalized salt is useful to the extent that one starts with a single initial product.
  • the starting salt is regenerated and therefore recycled.
  • the function F 0 of the starting salt can confer particular reaction activation properties on the medium, for example by hydrogen bonding or by any other activation dependent on the function F 0 .
  • the present invention relates to the use of an ionic liquid as defined above, characterized in that the A 2 + cation and/or the X 2 ⁇ anion of the functionalized salt(s), corresponding to a Y— ionic entity linked to at least one function F i , are immobilized in the liquid matrix and cannot be extracted from the liquid matrix by standard extraction means, in particular by solvent, and in which the function(s) F i of the functionalized salt(s) can be converted at the end of at least one reaction resulting from the addition of at least one reagent to said composition.
  • immobilized means that the functionalized salt cannot be extracted from the matrix by standard means such as extraction or distillation.
  • the present invention is based on the unexpected feature according to which the mixture of a functionalized salt in a A 1 + X 1 ⁇ liquid matrix results in the immobilization of said functionalized salt in said liquid matrix.
  • the present invention relates to the use of an ionic liquid as defined above, characterized in that several functionalized salts are immobilized.
  • the present invention relates to the use as defined above, characterized in that the A 2+ cation is functional.
  • the present invention relates to the use as defined above, characterized in that the A 2+ cation is functional and the X 2 ⁇ anion is non-functional.
  • the present invention relates to the use as defined above, characterized in that the X 2 ⁇ anion is functional.
  • the present invention relates to the use as defined above, characterized in that the X 2 ⁇ cation is functional and the A 2+ anion is non-functional.
  • the present invention relates to the use as defined above, characterized in that A 2+ and X 2 ⁇ are functional.
  • the present invention relates to the use as defined above, characterized in that:
  • either the ionic liquid of formula A 1 + X 1 ⁇ is solid at ambient temperature and is liquefiable within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C.
  • the A 2 + X 2 ⁇ functionalized salt is solid at ambient temperature and is soluble in the liquefied A 1 + X 1 ⁇ ionic liquid, in order to form a homogeneous phase
  • a 1 + X 1 ⁇ is solid at ambient temperature and is liquefiable within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C.
  • the A 2 + X 2 ⁇ functionalized salt is liquid at ambient temperature, and is miscible with the liquefied A 1 + X 1 ⁇ ionic liquid, in order to form a homogeneous phase
  • the A 1 + X 1 ⁇ ionic liquid is liquid at ambient temperature and the A 2 + X 2 ⁇ functionalized salt is liquid at ambient temperature and miscible with the A 1 + X 1 ⁇ ionic liquid, in order to form a homogeneous phase,
  • the A 1 + X 1 ⁇ ionic liquid is liquid at ambient temperature and the A 2 + X 2 ⁇ functionalized salt is solid at ambient temperature and is soluble or partially soluble in the A 1 + X 1 ⁇ ionic liquid within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C., in order to form a homogeneous phase.
  • a 2 + X 2 ⁇ is soluble in A 1 + X 1 ⁇ at a temperature higher than ambient temperature, which makes it necessary to work at this temperature in order to obtain a homogeneous phase and to avoid reprecipitation; if not, once the functionalized salt is dissolved, a solution is recovered at ambient temperature without reprecipitation;
  • a 2 + X 2 ⁇ functionalized salt in a standard solvent, to mix the solution with liquid A 1 + X 1 ⁇ , then to eliminate the solvent under vacuum in order to obtain a solution of A 2 + X 2 ⁇ .
  • the present invention relates to the use as defined above, characterized in that:
  • the ionic liquid of formula A 1 + X 1 ⁇ is solid at ambient temperature and is liquefiable within a temperature range from approximately 25° C. to approximately 250° C., in particular from approximately 30° C. to approximately 150° C.
  • the present invention also relates to the use as defined above, characterized in that the ionic liquid of formula A 1 + X 1 ⁇ , playing the role of liquid matrix, has a viscosity less than or equal to approximately 1500 cp (15 N.s/m 2 ), in particular less than approximately 500 cp (5 N.s/m 2 ) and preferably less than approximately 200 cp (2 N.s/m 2 ).
  • the present invention relates to a stable composition containing in solution:
  • the functionalized salt in particular the functionalized onium salt, being dissolved in the liquid matrix, in order to form a homogeneous phase
  • a 1 + representing a non-functional cation or a mixture of cations in which none of the cations is functional
  • X 1 ⁇ representing a non-functional anion or a mixture of anions in which none of the anions is functional
  • a 2 + representing a cation, functional or non-functional, or a mixture of cations in which none of the cations is functional or in which at least one of the cations is functional
  • X 2 ⁇ representing an anion, functional or non-functional, or a mixture of anions in which none of the anions is functional or in which at least one of the anions is functional
  • a 2 + and/or X 2 ⁇ represent(s) or comprise(s) a functional cation and a functional anion respectively,
  • the present invention relates to a stable composition containing in solution:
  • At least one second part of said ionic liquid of formula A 1 + X 1 ⁇ in which said initial function or functions F 0 are converted into first novel functions, conferring on said second part of said ionic liquid the role of functionalized salt and reaction support,.
  • a composition of the invention is characterized in that the A 2 + cation and/or the X 2 ⁇ anion of the functionalized salt or salts, corresponding to an ionic entity Y— linked to at least one function F i , are immobilized in the liquid matrix and cannot be extracted from the liquid matrix by standard means of extraction, in particular by solvent.
  • An advantageous composition of the present invention is characterized in that the liquid matrix is non-reactive vis-à-vis the functionalized salt.
  • the property of non-reactivity of the matrix vis-à-vis the salt is verified for example using the usual spectroscopic techniques such as 1 H, 13 C NMR, mass spectrometry, or HPLC analysis.
  • composition of the present invention is characterized in that A 2 + is a functional cation.
  • composition of the present invention is characterized in that the X 1 ⁇ and X 2 ⁇ anions are identical.
  • This particular case relates in particular to the case of large anions such as NTf 2 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CF 3 SO 3 ⁇ commonly used for the preparation of ionic liquids.
  • This particular embodiment also promotes the solubility of one salt in another.
  • composition of the present invention is characterized in that the X 1 ⁇ and X 2 ⁇ anions are different.
  • This particular case relates to the general case where a functionalized salt, for example a halide (Cl ⁇ , Br ⁇ , I ⁇ , F ⁇ ) is dissolved in an ionic liquid matrix.
  • a functionalized salt for example a halide (Cl ⁇ , Br ⁇ , I ⁇ , F ⁇ ) is dissolved in an ionic liquid matrix.
  • a functionalized salt for example a halide (Cl ⁇ , Br ⁇ , I ⁇ , F ⁇ ) is dissolved in an ionic liquid matrix.
  • This particular embodiment has the particular advantage of allowing the dissolution of inexpensive salts.
  • composition according to the present invention is characterized in that:
  • MX j a Lewis acid and a halide, preferably Cl ⁇ or F ⁇ , of general formula MX j , j being an integer comprised between 1 and 7, and M representing a metal, in particular chosen from aluminium, tin, zinc, bismuth, manganese, iron, copper, molybdenum, antimony, gallium or indium;
  • An advantageous composition of the present invention is characterized in that the A 2 + functional cation corresponds to a Y + — cationic entity, linked, optionally via an L arm, in particular an alkyl group comprising 1 to 20 carbon atoms, to a function F 0 , said function F 0 being chosen from the standard functions of organic chemistry, such as the hydroxyl, carboxylic, amide, sulphone, primary amine, secondary amine, aldehyde, ketone, ethenyl, ethynyl, dienyl, ether, epoxide, phosphine (primary, secondary or tertiary), azide, imine, ketene, cumulene, heterocumulene, thiol, thioether, sulphoxide, phosphorus-containing groups, heterocycles, sulphonic acid, silane, stannane or functional aryl functions.
  • organic chemistry such as the hydroxyl, carboxylic
  • a composition of the invention is characterized in that the ionic liquid is chosen from the following:
  • R a and R b representing linear or branched alkyl groups, comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group, or functional alkyl groups comprising 1 to 20 carbon atoms, or functional or non-functional aryl groups comprising 6 to 30 carbon atoms, Bu 3 P + —Me, X 1 ⁇ ⁇ P(C 6 H 13 ) 3 C 14 H 29 , X 1 ⁇ (C 8 H 17 ) 3 N + Me, X 1 ⁇
  • X 1 ⁇ being in particular chosen from: NTf 2 ⁇ , PF 6 ⁇ , BF 4 ⁇ or CF 3 SO 3 ⁇ .
  • X 2 ⁇ being chosen from: NTf 2 ⁇ , PF 6 ⁇ , BF 4 ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CF 3 SO 3 ⁇ , MeSO 4 ⁇ , EtSO 4 ⁇ , MeSO 3 ⁇ , C 6 H 5 SO 3 ⁇ , pMeC 6 H 4 SO 3 ⁇ ,
  • n being an integer comprised between 0 and 20
  • R ⁇ representing a substituted or non-substituted vinyl group, functional aryl group comprising 1 to 20 carbon atoms, or functional alkyl group comprising 6 to 30 carbon atoms,
  • R a representing a branched or non-branched alkyl group comprising 1 to 20 carbon atoms, in particular an ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group.
  • a composition of the invention is characterized in that X 2 ⁇ is a functional anion, corresponding in particular to an anion the pK A of the conjugated acid of which is less than 30, and is chosen in particular from the following anions: OH ⁇ , F ⁇ , R c BZ 3 ⁇ , N 3 ⁇ , CN ⁇ , or
  • Z representing an —F, —OH, —OR moiety
  • R representing an alkyl group comprising 1 to 20 carbon atoms
  • V and W representing, independently of one another, an electroattractive moiety, in particular a cyano, alkoxycarbonyl moiety comprising 2 to 20 carbon atoms, acyl moiety comprising 2 to 20 carbon atoms, benzoyl, alkyl sulphonyl moiety comprising 1 to 20 carbon atoms, aryl sulphonyl moiety comprising 6 to 30 carbon atoms, dialkoxyphosphonyl moiety comprising 2 to 20 carbon atoms,
  • R c representing a branched or non-branched, cyclic or non-cyclic alkyl moiety comprising 1 to 20 carbon atoms, or an aryl moiety comprising 6 to 30 carbon atoms,
  • a 2 + cation is chosen from the ammonium and phosphonium cations, in particular from the following cations: Me 3 N + —R d Et 3 N + —R d Bu 4 P + —R d
  • R d being an alkyl group comprising 1 to 20 carbon atoms.
  • the present invention also relates to the use of a composition as defined above, for continuous, discontinuous, combinatorial, or parallel organic synthesis, and/or for the preparation of libraries of products.
  • the present invention also relates to the use of a composition as defined above, for the implementation of a process for the preparation of a molecule G of an initial function F 0 , linked, optionally via an L arm, in particular an alkyl group comprising 1 to 20 carbon atoms, to a Y + -ionic entity, forming part of the A 2 + cation of the A 2 + X 2 ⁇ , and/or Y ⁇ — functionalized salt, forming part of the X 2 ⁇ anion of the A 2 + X 2 ⁇ functionalized salt, the cation being in the form Y + -L-F 0 and/or the anion being in the form Y ⁇ -(L) k -F 0 , k being equal to 0 or 1, which process comprises the steps:
  • the solutions are easily transferable using syringe and (or) pumping techniques
  • the present invention relates to the use as defined above, for implementation of the Diels-Alder reaction, according to one of the following reaction diagrams:
  • p being an integer varying from 0 to 2
  • Y + — representing an onium cation as defined above, and preferably being a trimethylalkylammonium, triethylalkylammonium or tributylalkylphosphonium cation,
  • L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group, comprising 6 to 30 carbon atoms, and preferably being a linear alkyl group preferably a linear alkyl group of (CH 2 ) r type, r varying from 1 to 20, and preferably from 3 to 6,
  • X 2 ⁇ being as defined above, and being in particular NTf 2 ⁇ , BF 4 ⁇ , PF 6 ⁇ , Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , CF 3 CO 2 ⁇ , CF 3 SO 3 ⁇ , BR 4 ⁇ , R being as defined above,
  • R a and R b being as defined above, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
  • X 1 ⁇ being chosen from: BF 4 ⁇ , PF 6 ⁇ , NTf 2 ⁇ , Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , CF 3 CO 2 ⁇ , CF 3 SO 3 ⁇ , BR 4 ⁇ , R being as defined above,
  • F 0 corresponds to a ⁇ 1 H group, in which ⁇ 1 represents an oxygen atom or an —NR f group, R f corresponding to a linear or branched alkyl group, comprising 1 to 20 carbon atoms, or an aryl group comprising 6 to 30 carbon atoms,
  • F 1 corresponds to the following formula: ⁇ 1 being as defined above,
  • F 2 corresponds to the following formula: ⁇ 1 being as defined above,
  • ⁇ 2 represents either an OR g group, R g representing a hydrogen atom or an alkyl group comprising 1 to 20 carbon atoms, or an —NR h R u group, R h and R u representing independently of one another a hydrogen atom, an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
  • F 0 represents any function making it possible to attach a 1,3-diene, and is in particular chosen from the carbonyl, amine, alkoxy, silane, stannane and borane functions, comprising 1 to 20 carbon atoms,
  • F 1 corresponds to the following formula: p being an integer varying from 0 to 2,
  • F 2 corresponds to the following formula: ⁇ 3 representing an electroattractive group, in particular chosen from the cyano, alkoxycarbonyl groups, comprising 1 to 20 carbon atoms, acyl group comprising 2 to 20 carbon atoms, benzoyl, sulphonyl, dialkoxyphosphonyl groups comprising 1 to 10 carbon atoms,
  • the present invention also relates to the use as defined above, for implementation of Heck's reaction, according to the following reaction diagram:
  • Y + — representing an onium cation as defined above, and preferably being a trimethylalkylammonium, triethylalkylanimonium or tributylalkylphosphonium cation,
  • L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group comprising 1 to 20 carbon atoms, and preferably being a linear alkyl group preferably a linear alkyl group of type (CH 2 ) r , r varying from 1 to 20, and preferably of 3 to 6,
  • X 2 ⁇ being as defined above, and being in particular BF 4 ⁇ , PF 6 ⁇ , NTf 2 ⁇ , CF 3 SO 3 ⁇ , Cl ⁇ , Br ⁇ , or I ⁇ ,
  • R a and R b being as defined above, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
  • X 1 ⁇ being chosen from: BF 4 ⁇ , PF 6 ⁇ , NTf 2 ⁇ , Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , CF 3 CO 2 ⁇ , CF 3 SO 3 ⁇ , BR 4 ⁇ , R being as defined above,
  • F 0 corresponds to a ⁇ 1 H group, in which ⁇ 1 represents an oxygen atom or a —NR f group, R f corresponding to a linear or branched alkyl group, comprising 1 to 20 carbon atoms, or an aryl group comprising 6 to 30 carbon atoms,
  • F 1 corresponds to the following formula: ⁇ 1 being as defined above,
  • F 2 corresponds to the following formula: ⁇ 1 being as defined above,
  • ⁇ 2 represents either an —OR g group, R g representing a hydrogen atom or an alkyl group comprising 1 to 20 carbon atoms, or an —NR h R u group, R h and R u representing independently of one another a hydrogen atom, an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
  • ⁇ 3 representing a leaving group, in particular chosen from the halides I, Cl and Br, the mesylate, tosylate, triflate, sulphonate, sulphate or phosphate groups,
  • T 1 , T 2 , T 3 , T 4 and T 5 representing independently of one another a hydrogen atom, a linear or branched alkyl group, comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms, or a functional group in particular chosen from NO 2 , CN, COOR, OR, COR, NHCOR, NRR′′, SO 2 R, I, Br, R and R′′ representing independently of one another an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
  • F′ 1 corresponds to the following formula: ⁇ 1 and ⁇ 3 being as defined above,
  • F′ 2 corresponds to the following formula: ⁇ 1 being as defined above,
  • G′ corresponding to the following formula: ⁇ 2 being as defined above.
  • the present invention relates to the use as defined above, for implementation of the Baylis-Hillman reaction, according to the following reaction diagram:
  • Y + — representing an onium cation as defined above, and preferably being a trimethylalkylammonium, triethylalkylammonium or tributylalkylphosphonium cation,
  • L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group, comprising 6 to 30 carbon atoms, and preferably being a linear alkyl group preferably a linear alkyl group of (CH2) r type, r varying from 1 to 20, and preferably from 3 to 6,
  • X 2 ⁇ being as defined above, and being in particular BF 4 ⁇ , PF 6 ⁇ , NTf 2 ⁇ , CF 3 SO 3 ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 CO 2 ⁇ or CF 3 CO 2 ⁇ ,
  • R a and R b being as defined above, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
  • X 1 ⁇ being chosen from: BF 4 ⁇ , PF 6 ⁇ , NTf 2 ⁇ , Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , CF 3 CO 2 ⁇ , CF 3 SO 3 ⁇ , BR 4 ⁇ , R being as defined above,
  • F 0 represents an —OH group
  • F 1 corresponds to the following formula:
  • G corresponding to the following formula: ⁇ 1 representing an —OH group, or an —OR g group, R g representing a linear or branched alkyl group, comprising 1 to 20 carbon atoms,
  • Ar representing a substituted or non-substituted, aromatic or heteroaromatic group ArCHO being in particular chosen from:
  • the present invention relates to use as defined above, for implementation of Suzuki coupling, according to one of the following reaction diagrams:
  • R 3 being chosen from the substituted or non-substituted aryl, heteroaryl, ethenyl, dienyl, allyl, ethynyl groups, comprising 2 to 30 carbon atoms,
  • R 7 represents a branched or linear alkyl group or a cycloalkyl group comprising 1 to 12 carbon atoms
  • Y + — representing an onium cation as defined above, and preferably being a trimethylalkylammonium, triethylalkylammonium or tributylalkylphosphonium cation,
  • L representing an arm, in particular a linear or branched alkyl group comprising 1 to 20 carbon atoms, or an optionally functional aralkyl group comprising 6 to 30 carbon atoms, and preferably being a linear alkyl group, preferably a linear alkyl group of (CH 2 ) r type, r varying from 2 to 20, and preferably from 3 to 6,
  • X 2 ⁇ being as defined above, and being in particular NTf 2 ⁇ , BF 4 ⁇ , PF 6 ⁇ , Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , CF 3 CO 2 ⁇ , CF 3 SO 3 ⁇ , BR 4 ⁇ , R being as defined above,
  • R a and R b being as defined above, and preferably representing alkyl groups comprising 1 to 20 carbon atoms,
  • X 1 ⁇ being chosen from: BF 4 ⁇ , PF 6 ⁇ , NTf 2 ⁇ , Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , CF 3 CO 2 ⁇ , CF 3 SO 3 ⁇ , BR 4 ⁇ , R being as defined above,
  • F 0 is in the form ⁇ 1 H, ⁇ 1 representing an oxygen atom or an —NR f group, R f corresponding to a linear or branched alkyl group, comprising 1 to 20 carbon atoms, or an aryl group comprising 6 to 30 carbon atoms,
  • F 1 is in the form —R e ⁇ , R e representing an aromatic or heteroaromatic group comprising 6 to 30 carbon atoms, ⁇ representing a leaving group preferably chosen from Cl, Br, I, OTf, O—CO 2 R 5 or OSO 3 —R 5 , R 5 representing an alkyl group comprising 1 to 10 carbon atoms or an aralkyl group comprising 6 to 30 carbon atoms, F 1 preferably corresponding to the following formula:
  • F 2 is in the form —R e —R 2 , R e being as defined above and R 2 being chosen from the substituted or non-substituted aryl, heteroaryl, ethenyl, dienyl, allyl, ethynyl groups, comprising 2 to 30 carbon atoms, F 2 preferably corresponding to the following formula:
  • Ar 1 representing an aromatic group preferably chosen from:
  • the G molecule being in the form R 2 —R 3 , R 2 and R 3 being as defined above, and corresponds in particular to the following formula:
  • ⁇ 2 represents either an —OR g group, R g representing a hydrogen atom or an alkyl group comprising 1 to 20 carbon atoms, or an —NR h R u group, R h and R u representing independently of one another a hydrogen atom, an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
  • Ar 1 is as defined above,
  • F 0 is in the form ⁇ 1 H, ⁇ 1 being as defined above,
  • F 1 is in the form —R q —B(OR 7 ) 2 , R 7 being as defined above, and R q corresponding to a substituted or non-substituted aryl group comprising 6 to 30 carbon atoms, heteroaryl group comprising 4 to 20 carbon atoms, ethenyl group comprising 2 to 20 carbon atoms, dienyl group comprising 3 to 20 carbon atoms, allyl group comprising 3 to 20 carbon atoms, ethynyl group comprising 2 to 20 carbon atoms, F 1 preferably corresponding to the following formula:
  • Ar 2 corresponding to a substituted or non-substituted aryl group comprising 6 to 30 carbon atoms
  • F 2 is in the form —R q —R e , R q and R e being as defined above, F 2 preferably corresponding to the following formula:
  • Ar 1 representing an aromatic group preferably chosen from:
  • the G molecule being in the form R 2 —R 3 , R 2 and R 3 being as defined above, and corresponding in particular to the following formula: in which ⁇ 2 , Ar 1 and Ar 2 are as defined above,
  • R 3 preferably being a phenyl group
  • a 2 + being an (R a ) 3 N + R b ammonium or (R a ) 3 P + R b phosphonium cation, preferably tetrabutylammonium and tetramethylammonium, R a and R b being as defined above,
  • X 2 ⁇ being in particular chosen from OH ⁇ , F ⁇ , CN ⁇ , RO ⁇ , RS ⁇ , preferably OH ⁇ or F ⁇ , R s representing an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
  • R 6 and R 7 representing independently of one another an alkyl group comprising 1 to 20 carbon atoms or an aryl group comprising 6 to 30 carbon atoms,
  • the boronic molecule of formula R 3 R 7 R 6 B being a trialkyl or aryl borane, the alkyl group comprising 1 to 20 carbon atoms and the aryl group comprising 6 to 30 carbon atoms, a boronic acid or ester, preferably a boronic acid or ester chosen as being phenyl boronic acid,
  • R 2 and ⁇ are as previously defined, R 2 ⁇ preferably corresponding to an aryl halide chosen from:
  • the present invention also relates to the use as defined above, for the synthesis of libraries of molecules according to the parallel-synthesis technique, according to the following diagram:
  • Y + -L-F 1 , X 2 ⁇ functionalized salt in the A 1 + , X 1 ⁇ ionic liquid is separated into n approximately equal parts, n varying from 2 to 1024, and in that each of these parts is then converted according to an organic-synthesis reaction, preferably a Heck or Suzuki coupling reaction, each using a different reagent B i in order to produce n solutions each containing a defined Y + -L-F 2 i , X 2 ⁇ compound, F 2 i representing a function chosen from the functions as defined above, i varying from 1 to n, each solution being treated in order to release the G i molecules, i varying from 1 to n, which are each isolated and purified, constituting a molecule library.
  • an organic-synthesis reaction preferably a Heck or Suzuki coupling reaction
  • the parallel-synthesis technique consists of preparing in parallel and simultaneously libraries of perfectly identified single products at a rate of one product per reactor or per well, after a sequence of reactions carried out with reagents specific to each prepared product.
  • molecule library designates a set of products all identified, not mixed, each of them being arranged in its own container. This type of molecule library results from parallel synthesis. This expression can also designate a mixture of products identified by analysis techniques at the disposal of chemists and resulting from the reaction of a mixture of reagents with a single product or of a mixture of products with a single reagent according to the split-and-mix technique.
  • the present invention also relates to the use as defined above, for implementation of the synthesis of molecule libraries by the split-and-mix technique according to the following diagram:
  • n fractions of the Y + -L-F 1 , X 2 ⁇ solution, obtained from the starting Y + -L-F 0 , X 2 ⁇ functionalized salt, in the A 1 + X 1 ⁇ ⁇ ionic liquid are converted in parallel according to an organic chemistry reaction, preferably a Heck or Suzuki coupling reaction, each using a different reagent B i in order to produce n solutions each containing a defined Y + -L-F 2 i , X 2 ⁇ compound, i varying from 1 to n, n varying from 2 to 1024, preferably from 2 to 96, F 2 i representing a function chosen from the functions as defined above,
  • the mixture as obtained in the preceding step is separated from the A 1 + X 1 ⁇ ionic liquid and from the starting Y + -L-F 0 , X 2 ⁇ functionalized salt by the usual separation methods, preferably by vacuum distillation, by extraction with a standard solvent such as heptane or toluene followed by evaporation of solvent, by chromatography on a column, plates or under pressure, in order to obtain a library containing n G i molecules,
  • the split-and-mix technique (O'Brecht et al., 1998) consists of reacting n fractions of a solution of a product, each with a different reagent leading to n novel products which are mixed after identification. This novel mixture is separated into m fractions which are then reacted in parallel each with a different reagent leading to m mixtures of n novel products, i.e. m ⁇ n products. These operations are repeated as many times as necessary.
  • FIG. 1 represents proton NMR spectra recorded at 200 MHz in acetone D6, corresponding to monitoring of the Heck coupling reaction between the supported acrylate 6 and 1-iodonaphthalene.
  • FIG. 2 represents a chromatogram corresponding to the mixture of the nine methyl esters 13a to 13i the mass spectra of which are described in Table II.
  • FIG. 3 represents a chromatogram corresponding to the mixture of the nine ethyl esters 14a to 14i the mass spectra of which are described in Table III.
  • FIG. 4 represents a chromatogram corresponding to the mixture of the nine propyl esters 15a to 15i the mass spectra of which are described in Table IV.
  • FIG. 5 represents a chromatogram corresponding to the mixture of the nine butyl esters 16a to 16i the mass spectra of which are described in Table V.
  • FIG. 6 represents proton NMR spectra recorded at 200 MHz in acetone D6, corresponding to monitoring of the Heck coupling reaction between the supported aryl iodide 7 and tertbutyl acrylate.
  • the upper spectrum corresponds to the spectrum of 7b in 0.85 M solution in Me 3 N—(CH 2 ) 2 Me,NTf 2 ⁇ .
  • the lower spectrum is that of the reaction mixture once the Heck coupling is finished.
  • FIG. 7 represents a chromatogram corresponding to the mixture of the biaryl propyl esters 23a to 23i the mass spectra of which are described in Table XI.
  • FIG. 8 represents a chromatogram corresponding to the mixture of the biaryl methyl esters of Table XII.
  • FIG. 9 represents a chromatogram corresponding to the mixture of the biaryl ethyl esters of Table XIII.
  • FIG. 10 represents proton NMR spectra recorded at 200 MHz in acetone D6, corresponding to monitoring of Grieco's reaction with supported aniline 1 and 4-nitrobenzaldehyde.
  • FIG. 12 represents a chromatogram corresponding to the mixture of the methyl esters the mass spectra of which are described in Table XX.
  • FIG. 13 represents a chromatogram corresponding to the mixture of the ethyl esters the mass spectra of which are described in Table XXI.
  • a solution of 10 g of ammonium salt (1a) (65.3 mol) in 10 mL of water is prepared in a beaker.
  • 20 g of lithium bis-trifluoromethanesulphonamide (71.9 mmol) is dissolved in the same manner.
  • the two solutions are mixed and stirred for 2 hours at ambient temperature in order for the exchange to be complete.
  • the two phases obtained are separated in a separating funnel, and the aqueous phase is extracted twice with 15 ml of methylene chloride. Finally, the solvent is evaporated and the product is dried under vacuum.
  • the solid thus obtained is dissolved in 15 ml of a solution of hydrobromic acid (6 N), then taken to reflux for 12 hours, followed by evaporation to dryness.
  • the solid obtained is washed in ether and then dried under vacuum.
  • the contents of the beaker are decanted into a separating funnel.
  • the aqueous phase is extracted with twice 15 mL of methylene chloride.
  • the organic phases are collected and dried over MgSO 4 .
  • the solvent is then evaporated to dryness and the product is dried under vacuum.
  • the solid obtained is dissolved in acetone, filtered on MgSO 4 , and evaporated to dryness. A white solid is obtained which is dried in a desiccator under vacuum in the presence of P 2 O 5 .
  • the contents of the beaker are decanted into a separating funnel and the aqueous phase is extracted with twice 15 mL of methylene chloride.
  • the 2 organic phases are collected and dried over MgSO 4 .
  • the solvent is then evaporated to dryness and the product is dried under vacuum.
  • a solution of N,N′,N′′-trimethyl-3-hydroxypropylammonium salt and 3 equivalents of acryloyl chloride in acetonitrile is stirred in the presence of 5 equivalents of solid K 2 CO 3 for 2 hours at a temperature comprised between 18 and 22° C.
  • the mixture is then filtered and placed under vacuum in order to eliminate the solvent and the excess of the reagent.
  • the ammonium acrylate thus obtained is stable at 4° C. and can be stored for several months.
  • the medium becomes biphasic, the upper phase is eliminated and the white paste is washed 3 times with 20 ml of anhydrous ether.
  • tetrabutylammonium hydroxide 0.1 g (0.38 mmol) of tetrabutylammonium hydroxide is dissolved in 0.6 g of N,N′,N′′-trimethylbutylammonium bis-trifluoromethanesulphonamide as matrix in a 5-ml flask. 47 mg (0.38 mmol) of phenylboronic acid and finally 0.5 mL of THF (anhydrous) are added to this solution. The solution is left under stirring for 2 hours at ambient temperature. Then the THF is evaporated to dryness and the solution is dried under vacuum.
  • THF anhydrous
  • anhydrous tetramethylammoniun fluoride 0.1 g (2.1 mmol) of anhydrous tetramethylammoniun fluoride is introduced into a 10-mL single-necked flask, then 1 mL of THF (anhydrous) is added and the solution is homogenized while heating if necessary. Finally, 0.13 g of phenylboronic acid (2.1 mmol) is introduced. Stirring is maintained for approximately 2 hours at ambient temperature.
  • an arylboronic acid ester in the form of boratrane (functionalization of the cationic part) or in the form of borate (functionalization of the anionic part of the functionalized salt).
  • acryl ester and an acryl ester substituted by an iodine atom are separately used as substrates.
  • the acrylate (6) was involved in Heck in the presence of palladium acetate as catalyst, potassium bicarbonate as base and an aryl iodide in large excess as reagent (see diagram hereafter).
  • FIG. 1 shows the example of the reaction of the salt 6 (X 2 ⁇ ⁇ NTf 2 ⁇ ) in solution in trimethylbutylammonium triflimide with 1-iodonaphthalene (test 10 in Table I below).
  • FIG. 1 it is noted that it is possible and simple to monitor the reaction by 1 H NMR. In fact, the total disappearance of signals between 5.9 and 6.5 ppm is noted corresponding to the three protons of the double bond of the substrate 6, and the appearance of signals of the double bond of the product resulting from the Heck coupling 12.
  • transesterification was carried out with different alcohols on a mixture of the products 12a to 12i isolated during the last stage, according to the procedure below.
  • the alcohols used are methanol, ethanol, propanol and butanol.
  • each solution is evaporated to dryness and the different mixtures are separately extracted with 3 times 15 ml of diethyl ether.
  • the products extracted are then analyzed in MS-GPC, and the chromatograms corresponding to each mixture are presented below.
  • Compounds 13a to 13i corresponds to the product of formula in which R is a methyl group.
  • Compounds 14a to 14i correspond to the product of formula in which R is an ethyl group.
  • Table III shows these 9 ethyl esters, indicating for each the meaning of Ar. This table corresponds to the chromatogram of FIG. 3 .
  • TABLE III Retention time (min) Mass found 14 Ar 13.136 194 14a 13.196 176 14b 13.800 13.980 14.087 190 14c 14d 14e 15.475 254 14f 15.577 206 14g 16.318 221 14h 19.434 226 14i
  • Table IV below shows these 9 propyl esters, indicating for each the meaning of Ar. This table corresponds to the chromatogram of FIG. 4 .
  • Compounds 16a to 16i correspond to the product of formula in which R is a butyl group.
  • the second example of functionalized salt which was tested in the Heck reaction is an aryl iodide supported on (TMHPA, NTf 2 ) (1) according to the following diagram:
  • FIG. 6 illustrates and confirms the simplicity of monitoring by this analysis technique, a more difficult matter in the case of the solid or soluble supports described in the literature.
  • the first recycling of the functionalized salt leads to a yield of 88%.
  • the Diels-Alder reaction between a dienophile 6 and cyclopentadiene was therefore studied.
  • the diagram hereafter represents the different stages.
  • the regiospecificity of this reaction is comparable to that observed in the case of the non-supported substrate, i.e. methyl acrylate.
  • the third example used in order to validate the OSSIL principle is the Baylis-Hillman reaction, which consists of the condensation of an aldehyde on the double bond of the acrylic substrate 6 in the presence of 3-hydroxyquinuclidine (see diagram hereafter).
  • a mixture of 2 mmol of 6 and 10 mmoles of aldehyde in a solvent or an ionic matrix is stirred at ambient temperature in the presence of 2 mmoles of 3-nuclidine hydroxyquinuclidine as base.
  • Another example where we applied the OSSIL principle is the Suzuki coupling reaction which consists of the coupling of an aryl halide and an aryl boronic acid.
  • ii the functionalized salt is used pure and serves as ionic matrix.
  • iii TEA triethylamine.
  • iv TEAS tertiary amine of formula: Me 3 N + (CH 2 ) 2 CH 2 NEt 2 , NTf 2 ⁇
  • Tests 1 to 4 show that the reactivity of the functionalized salts (ionic supports) the anion of which is tetrafluoroborate or hexafluorophosphate is much greater than that observed with a chloride or bis-trifluoromethanesulphonamide anion.
  • the fact that all the ionic supports are dissolved in the same matrix proves that, from the point of view of the mechanism, it is the ionic part of the support which is probably involved at the level of the palladium. This observed reactivity is moreover accompanied by a very great selectivity in the case of the tetrafluoroborate anion.
  • tests 1 to 4 show that the mixture of salts carrying different cations or anions do not at all reduce either the reactivity or the selectivity, which offers a wide choice and makes it possible to reduce the cost of the cations and of anions which is sometimes considerable: a chloride costs perhaps 50 times less, for example, than a triflimide.
  • This library of biaryl esters was prepared by operating as in the case of Example 1.
  • a first phase we carried out a series of coupling reactions in parallel with 9 arylboronic acids and supported 4-bromobenzoic acid. Then, the 9 reactions were mixed in order to form a homogeneous solution, which was then divided into three equal portions, after which each of the solutions was solubilized in an alcohol. Then a few drops of concentrated hydrochloric acid (12 N) were added and the alcohol was taken to reflux for 18 hours. After evaporation of the alcohol, the mixture of the biarylesters was extracted with ether. 3 series of 9 esters were therefore obtained which were then analyzed by GC/MS. The different expected biarylesters were all identified without ambiguity.
  • Table XI hereafter corresponds to the chromatogram of FIG. 7 .
  • the first one is to support an arylboronic acid on the cation of the salt functionalized by diethanolamine in order to form boratranes (see below):
  • the second one is to support it by means of the anion of the functionalized salt.
  • the X 2 ⁇ anion of the functionalized salt serving as support is nucleophilic enough, it will react with phenylboronic acid, quaternizing the boron atom in order to produce a borate:
  • the condensation reaction of trimethylamine on an alkyl dibromide is carried out under anhydrous conditions with very good yields (>95%).
  • the ammonium bromide thus obtained undergoes an anion-exchange reaction (metathesis) under standard conditions.
  • the second stage was carried out in the presence of an equivalent of diethanolamine with a quantitative yield.
  • the stage of grafting of the arylboronic acid was carried out with good yields and makes it possible to obtain a product in two different forms. In fact, as a function of the solvent and of the anion of the support, equilibrium is or is not obtained between the tri- and tetravalent borons.
  • the cationic part of the salt with a dedicated task was functionalized in order to support an arylboronic acid in the form of a boratrane with a tetravalent boron atom.
  • the latter represents the intermediate species in the Suzuki coupling reaction.
  • salts with nucleophilic anions OH ⁇ and F ⁇ ) capable of quaternizing the boron atom of arylboronic acid in order to produce borates, derivatives of tetravalent boron, an intermediate in the Suzuki coupling reaction.
  • the following commercial ammonium salts were therefore used:
  • the Bu 4 N + OH ⁇ dried under vacuum after evaporation of the water, is solubilized in the TMBA bis-trifluoromethanesulphonamide serving as matrix in order to produce a 0.85 mol/l solution.
  • a stoichiometric quantity of phenylboronic acid in solution in anhydrous THF is added to this solution at ambient temperature.
  • the monitoring of the reaction by 11 B NMR after evaporation of the THF shows that it is complete after two hours. A single signal is then observed at 3.97 ppm corresponding to a borate.
  • the salt was solubilized in THF (anhydrous) at ambient temperature, then phenylboronic acid was added. After 18 hours of stirring of the mixture at ambient temperature, the precipitate which forms is filtered then washed with ether.
  • the yield of isolated product depends on the quantity of phenylboronic acid used. In fact, in the presence of an excess of the latter, an 82% yield is obtained. On the other hand a deficiency causes it to drop to less than 50%.
  • the monitoring of this reaction is carried out using NMR of the boron and of the fluorine.
  • the melting point of the functionalized ionic salt/ionic matrix mixture must be below the reaction temperature
  • a matrix with a dedicated task (ionic matrix+functionalized salt) must preferably be soluble in the solvent.
  • N-methyl, N′-ethylimidazolium hexafluorophosphate (EMIM, PF 6 ) was used as ionic matrix, the melting point of which is of the order of 56° C.
  • 1 mmol of functionalized ionic salt (7a) is mixed with 1 g of the ionic matrix and heated to 70° C. in order to obtain a solution. On cooling down, this homogeneous mixture is solid at ambient temperature. On reheating and from 65° C., the medium again becomes liquid and completely homogeneous. The base and the catalyst are added to this solution like for the different tests mentioned above, followed by heating to 80° C. After 5 hours the 1 H NMR of the mixture shows complete disappearance of the starting iodide.
  • reaction mixture is cooled down to ambient temperature and a heterogeneous (solid/liquid) mixture is obtained. Then, ether is added and the solid is filtered out, then washed again in order to extract all of the acrylate.
  • the product is then released from the functionalized salt by transesterification according to the procedure described in the different examples mentioned above. After elimination under vacuum of the excess methanol, the cinnamic ester is isolated by the addition of ether and filtration of the solid mixture constituted by the functionalized salt and the starting solid matrix which can be reused.
  • FIG. 11 illustrates the simplicity of the monitoring of the reaction by proton NMR (Case of R ⁇ Ph).
  • the cleavage of the products after coupling was carried out by two transesterification processes, one by methanol, the other by ethanol.
  • the products of tests 4, 5, 6, 7 and 8 are mixed and reacted according to the “split-and-mix” principle in the presence of alcohol and a catalytic quantity of hydrochloric acid.
  • This stage also allows the recycling of the salt with a dedicated task as well as that of the matrix used for the reaction.
  • Table XX hereafter corresponds to the chromatogram of FIG. 12 .
  • MCRs Multi-Component Reactions
  • Multi-component reactions simultaneously bring at least three reaction partners into contact under experimental conditions which do not vary over time and allow the creation of several covalent bonds in a single stage, unlike standard reactions where two reagents lead to a product by the creation of new bonds.
  • MCRs combine convergence and economy of atoms, two fundamental principles in organic synthesis which are important for combinatorial chemistry.
  • these reactions generally take place with a high yield, since they avoid the succession of stages which, at each step, causes the yield to drop.
  • MCRs those of Passerini and Ugi (Ugi, 1976).
  • One of the key elements of these reactions is an isonitrile, the electronic structure of which, comprising a doublet and an electron hole, allows the passage of a formally divalent carbon atom to a tetravalent carbon atom by adding an electrophile and a nucleophile.
  • the diagram below presents an example of a Passerini reaction.
  • MCRs were transposed onto solid support, for example a resin with an amine termination was used in an Ugi-type reaction in order to produce, after cleavage, a series of high-purity adducts with yields ranging from average to excellent (see diagram below) (Lhoel and Nielsen, 1999).
  • the substituted quinolines are useful pharmacophores. Their synthesis on solid support was carried out by a so-called Doebner MCR, involving an aniline, an aldehyde and an ⁇ -dicarbonylated compound (see diagram hereafter) (Gopalsamy and Pallai, 1997). The quinolines are obtained with a high purity and very good yields.
  • the aniline 1 was supported and used with an aldehyde and cyclopentadiene in the presence of butyltrimethylammoniumtriflimide as matrix in order to produce tetrahydroquinolines (see diagram hereafter).
  • This example with three components, consists of a first condensation of the aldehyde and the aniline in order to produce the imine. The latter then reacts in what is formally a Diels-Alder reaction with cyclopentadiene in the presence of a catalytic quantity of trifluoroacetic acid.
  • FIG. 10 illustrates the case of 4-nitrobenzaldehyde, after washing with ether in order to eliminate the excess of the two reagents and the trifluoroacetic acid. This figure also shows that the monitoring of a reaction which leads to complex compounds is possible and with remarkable clarity. It should also be noted that transesterification by methanol leads to very clean products which are extracted with ether and purified by filtration on silica.
  • the viscous oil obtained is then dissolved in methanol and taken to reflux in the presence of 3 drops of concentrated hydrochloric acid. After 12 hours the product is extracted with ether (2 ⁇ 30 ml) after evaporation of the methanol.

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US20090326228A1 (en) 2009-12-31
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US9452425B2 (en) 2016-09-27
CA2500206A1 (fr) 2004-04-08
FR2845084B1 (fr) 2009-07-17
DE60310737T2 (de) 2008-03-20
FR2845084A1 (fr) 2004-04-02
AU2003276363A8 (en) 2004-04-19
JP2006500418A (ja) 2006-01-05
WO2004029004A1 (fr) 2004-04-08
EP1542942A1 (de) 2005-06-22
CA2500206C (fr) 2013-06-11
ATE349407T1 (de) 2007-01-15

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