WO1994017080A1 - Silaformylation d'aldehydes catalysee au rhodium et produits ainsi obtenus - Google Patents

Silaformylation d'aldehydes catalysee au rhodium et produits ainsi obtenus Download PDF

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Publication number
WO1994017080A1
WO1994017080A1 PCT/US1993/000781 US9300781W WO9417080A1 WO 1994017080 A1 WO1994017080 A1 WO 1994017080A1 US 9300781 W US9300781 W US 9300781W WO 9417080 A1 WO9417080 A1 WO 9417080A1
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WIPO (PCT)
Prior art keywords
cho
compound
formula
nmr
aldehydes
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PCT/US1993/000781
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English (en)
Inventor
Michael E. Wright
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Utah State University
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Utah State University
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Priority to PCT/US1993/000781 priority Critical patent/WO1994017080A1/fr
Publication of WO1994017080A1 publication Critical patent/WO1994017080A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • the invention relates to a method for preparing chiral and achiral ⁇ -silyloxyaldehydes.
  • the invention relates to a process for silaformylating aldehydes with a silicon hydride and carbon monoxide in the presence of a rhodium catalyst.
  • the invention includes a process wherein aldehydes of the formula: R-CHO, (I) are reacted with a silane of the formula:
  • R is a substituted or unsubstituted alkyl, aryl, aralkyl, or heterocyclic hydrocarbon.
  • the invention also includes a process for synthesizing compounds of specific relative stereochemis ⁇ try by reacting aldehydes of the formula:
  • R is aryl and R J can be alkyl, aryl, aralkyl, dialkylamino, or alkoxy radicals, with silane reagent of formula (II) and carbon monoxide in the presence of catalyst.
  • the ⁇ -silyloxyaldehydes are useful, for among other things, as intermediates, and can be convert ⁇ ed to ⁇ -silyloximine derivatives which are useful syn ⁇ thetic intermediates in the diastereoselective synthesis of 3-aminoalcohols.
  • the aldehyde used in the process will generally be chosen for its constituent R group.
  • the R group will be selected from the group of substituted or unsubstituted phenyl, lower (Cl to C4) alkyl, furanyl, pyrrolyl, and thiophenyl.
  • alkyl is preferably a saturated or unsaturated, branched or unbranched hydrocarbon having one to twenty carbon atoms, e.g. methyl, ethyl, isopentyl, and allyl.
  • Alkoxy groups will typically have one to four carbon atoms and include groups such as methoxy and ethoxy.
  • Aryl as used herein, is an aromatic hydrocarbon group, preferably having six to ten carbon atoms, such as phenyl or naphthyl.
  • Aralkyl is an arene group (having both aliphatic and aromatic portions) , preferably having seven to thirteen carbon atoms, such as benzyl, ethyl- benzyl, n-propylbenzyl, or isobutylbenzyl.
  • substitution with regard to the various R moi ⁇ eties generally relates to substituting a group such as alkoxy, halogen, hydroxy, nitro, or lower alkyl onto an aromatic ring for a hydrogen that would normally be pres- ent. Substitutions can also be made on an alkyl or alkoxy chain.
  • Halogen as used herein, generally refers to fluo ⁇ rine, chlorine, bromine or iodine.
  • rhodium complexes can be used as a catalyst.
  • Preferred rhodium catalysts for the silaformylation of aldehydes are rhodium cyclo ⁇ ctadiene chloride ([ (COD)RhCl] 2 ) or a compound of the formula:
  • silaformylation reaction Preferably, strong electron-withdrawing substituents will be avoided in the silaformylation reaction.
  • jD-nitrobenzaldehyde shows only a 40% conversion with only some silaformylation product (20% yield) .
  • Pyridine carboxaldehydes both the 2- and 4- were to be completely unreactive under the reaction conditions.
  • Preferred temperature ranges for the reaction vary from 0°C to 25°C.
  • the rhodium catalyzed silaformylation is selective for the aldehyde functionality in the presence of an ester. Highly functionalized aromatic compounds have been isolated in 70% yield. Spectral data collected from the crude reaction mixture indicated complete chemo- selectivity for the aldehyde group.
  • benzaldehyde, 4-bromobenzaldehyde, 4-dimethylamino- benzaldehyde, l-methyl-2-pyrrolecarboxaldehyde, 2- thiophenecarboxaldehyde, butyraldehyde, isobutyraldehyde, 2-furaldehyde, and ferrocenecarboxaldehyde were purchased from Aldrich Chemical Co. and used as received.
  • Dimethylphenylsilane, triethylsilane, triphenylsilane was purchased from H ⁇ ls America, Inc. and used as received.
  • the [ (COS)RhCl] 2 , 4-acetoxybenzaldehyde, and 4-(trimethyl- silyloy) benzaldehyde were prepared from literature pro- cedures. Giordano, G. ; Crabtree, R.H. , Inorg. Synth.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

Des aldéhydes substitués par des radicaux carbone tels que alkyle, aromatique et hétérocyclique, peuvent être silaformylés avec un réactif au silane et du monoxyde de carbone, en présence de rhodium comme catalyseur, pour produire des alpha-silyloxyaldéhydes. Les alpha-silyloxyaldéhydes sont des intermédiaires utiles dans la synthèse de molécules biologiquement actives.
PCT/US1993/000781 1993-01-26 1993-01-26 Silaformylation d'aldehydes catalysee au rhodium et produits ainsi obtenus Ceased WO1994017080A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US1993/000781 WO1994017080A1 (fr) 1993-01-26 1993-01-26 Silaformylation d'aldehydes catalysee au rhodium et produits ainsi obtenus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1993/000781 WO1994017080A1 (fr) 1993-01-26 1993-01-26 Silaformylation d'aldehydes catalysee au rhodium et produits ainsi obtenus

Publications (1)

Publication Number Publication Date
WO1994017080A1 true WO1994017080A1 (fr) 1994-08-04

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PCT/US1993/000781 Ceased WO1994017080A1 (fr) 1993-01-26 1993-01-26 Silaformylation d'aldehydes catalysee au rhodium et produits ainsi obtenus

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WO (1) WO1994017080A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004085414A1 (fr) * 2003-03-26 2004-10-07 Pharmacia & Upjohn Company Llc Procede de preparation d'1-aryl- et d'1-heteroaryl-2-aminoethanols enrichis en enantiomeres
US7262315B2 (en) * 2001-05-22 2007-08-28 California Institute Of Technology Transition metal oxo, sulfido and amido complexes as catalysts of nucleophilic addition reactions
CN119859163A (zh) * 2025-03-25 2025-04-22 中山大学 一种4-位取代呋喃苏糖衍生物的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803637A (en) * 1954-01-18 1957-08-20 Dow Corning Organosiloxane aldehydes
US4383120A (en) * 1981-07-17 1983-05-10 The Dow Chemical Company Thermal catalytic hydrosilylation of carbonyl compounds
US4424392A (en) * 1982-03-24 1984-01-03 Union Carbide Corporation Aldehyde containing hydrolyzable silanes
US4448980A (en) * 1983-09-22 1984-05-15 E. I. Du Pont De Nemours And Company Preparation of trialkylsilyl ethers
US4783543A (en) * 1987-11-23 1988-11-08 Dow Corning Corporation Process to produce silyl ketene acetals
US4785126A (en) * 1985-04-26 1988-11-15 E. I. Du Pont De Nemours And Company 1,4-O-metallation process and composition
US5124468A (en) * 1991-08-02 1992-06-23 General Electric Company Method for silylformylating alkynes and products obtained therefrom

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803637A (en) * 1954-01-18 1957-08-20 Dow Corning Organosiloxane aldehydes
US4383120A (en) * 1981-07-17 1983-05-10 The Dow Chemical Company Thermal catalytic hydrosilylation of carbonyl compounds
US4424392A (en) * 1982-03-24 1984-01-03 Union Carbide Corporation Aldehyde containing hydrolyzable silanes
US4448980A (en) * 1983-09-22 1984-05-15 E. I. Du Pont De Nemours And Company Preparation of trialkylsilyl ethers
US4785126A (en) * 1985-04-26 1988-11-15 E. I. Du Pont De Nemours And Company 1,4-O-metallation process and composition
US4783543A (en) * 1987-11-23 1988-11-08 Dow Corning Corporation Process to produce silyl ketene acetals
US5124468A (en) * 1991-08-02 1992-06-23 General Electric Company Method for silylformylating alkynes and products obtained therefrom

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7262315B2 (en) * 2001-05-22 2007-08-28 California Institute Of Technology Transition metal oxo, sulfido and amido complexes as catalysts of nucleophilic addition reactions
WO2004085414A1 (fr) * 2003-03-26 2004-10-07 Pharmacia & Upjohn Company Llc Procede de preparation d'1-aryl- et d'1-heteroaryl-2-aminoethanols enrichis en enantiomeres
CN119859163A (zh) * 2025-03-25 2025-04-22 中山大学 一种4-位取代呋喃苏糖衍生物的制备方法

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