WO2005012209A2 - Transformation enantio-selective catalysee d'alcenes - Google Patents

Transformation enantio-selective catalysee d'alcenes Download PDF

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Publication number
WO2005012209A2
WO2005012209A2 PCT/US2004/018649 US2004018649W WO2005012209A2 WO 2005012209 A2 WO2005012209 A2 WO 2005012209A2 US 2004018649 W US2004018649 W US 2004018649W WO 2005012209 A2 WO2005012209 A2 WO 2005012209A2
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substituted
group
diol
aryl
reaction
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WO2005012209A3 (fr
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James P. Morken
Jeremy B. Morgan
Nicholas F. Pelz
Steven P. Miller
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University of North Carolina at Chapel Hill
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University of North Carolina at Chapel Hill
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
    • C07C47/57—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/24—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
    • C07C49/245—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane

Definitions

  • Figure 12 is a chiral GLC ( ⁇ -dex, Supelco, 120 °C) analysis of diol product: (R)-decane-l , 2-diol.
  • Figure 13 is a chiral GLC ( ⁇ -dex, Supelco, 120 °C) analysis of diol product: (R)-3,3-Dimethyl-butane-1 , 2-diol.
  • Figure 14 is a chiral GLC ( ⁇ -dex, Supelco, 110 °C) analysis of diol product: (R)-3,3-Dimethyl-heptane-1 , 2-diol.
  • the structural formula also is presented.
  • Scheme 2 Formation of a reactive organometallic intermediate via (1) a catalytic asymmetric alkene dimetalation reaction and (2) a catalytic hydrogenation of a vinyl dimetallic substrate (2a) or a vinyl monometallic substrate (2b).
  • the reactive organometallic intermediate can undergo further reaction with a functionalized reagent to provide an optically active multifunctional compound.
  • the cycloalkyl group also can be optionally substituted with an alkyl group substituent as defined herein, oxo, and/or alkylene. There can be optionally inserted along the cyclic alkyl chain one or more oxygen, sulfur or substituted or unsubstituted nitrogen atoms, wherein the nitrogen substituent is hydrogen, alkyl (e.g., lower alkyl), or aryl, thus providing a cycloheteroalkyl group.
  • Representative monocyclic cycloalkyl rings include cyclopentyl, cyclohexyl, and cycloheptyl.
  • amino refers to the -NH 2 group.
  • carboxyl refers to the -COOH group.
  • halo refers to fluoro, chloro, bromo, and iodo groups.
  • hydroxyl refers to the -OH group.
  • hydroxyalkyl refers to an alkyl group substituted with an - OH group.
  • mercapto refers to the -SH group.
  • oxo refers to a compound described previously herein wherein a carbon atom is replaced by an oxygen atom.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne des réactions énantio-sélectives catalytiques qui agissent directement sur des alcènes non activés pour la préparation de blocs de construction organiques chiraux et de nouveaux matériaux. Plus particulièrement, il s'agit d'une réaction énantio-sélective catalysée agissant sur un hydrocarbure tel qu'un alcène et qui produit un intermédiaire organo-métallique réactif énantiomériquement enrichi pouvant être transformé en divers produits de réaction multifonctions optiquement actifs.
PCT/US2004/018649 2003-06-10 2004-06-10 Transformation enantio-selective catalysee d'alcenes Ceased WO2005012209A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US47725303P 2003-06-10 2003-06-10
US60/477,253 2003-06-10
US56626704P 2004-04-29 2004-04-29
US60/566,267 2004-04-29

Publications (2)

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WO2005012209A2 true WO2005012209A2 (fr) 2005-02-10
WO2005012209A3 WO2005012209A3 (fr) 2005-08-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108303385A (zh) * 2017-10-21 2018-07-20 聊城煤武新材料科技有限公司 一种测定双膦配体铑催化剂中铑含量的方法
CN109021013A (zh) * 2017-06-08 2018-12-18 中国科学技术大学 杂环芳烃取代的膦磺酸钯和镍催化剂及其配体、制备方法和用途
US10266503B1 (en) 2016-05-24 2019-04-23 The Board Of Trustees Of The University Of Illinois Sulfoxide ligand metal catalyzed oxidation of olefins
CN118239990A (zh) * 2024-05-28 2024-06-25 北京元延医药科技股份有限公司 不对称氢化催化合成药物的稀有贵金属和手性膦的配合物
WO2024227909A1 (fr) * 2023-05-03 2024-11-07 Firmenich Sa Semi-hydrogénation sélective d'allène

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5637739A (en) * 1990-03-21 1997-06-10 Research Corporation Technologies, Inc. Chiral catalysts and catalytic epoxidation catalyzed thereby
US6440745B1 (en) * 1994-10-18 2002-08-27 Symyx Technologies Combinatorial synthesis and screening of organometallic compounds and catalysts
US5665890A (en) * 1995-03-14 1997-09-09 President And Fellows Of Harvard College Stereoselective ring opening reactions
US6262278B1 (en) * 1995-03-14 2001-07-17 President And Fellows Of Harvard College Stereoselective ring opening reactions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10266503B1 (en) 2016-05-24 2019-04-23 The Board Of Trustees Of The University Of Illinois Sulfoxide ligand metal catalyzed oxidation of olefins
CN109021013A (zh) * 2017-06-08 2018-12-18 中国科学技术大学 杂环芳烃取代的膦磺酸钯和镍催化剂及其配体、制备方法和用途
CN109021013B (zh) * 2017-06-08 2020-05-12 中国科学技术大学 杂环芳烃取代的膦磺酸钯和镍催化剂及其配体、制备方法和用途
CN108303385A (zh) * 2017-10-21 2018-07-20 聊城煤武新材料科技有限公司 一种测定双膦配体铑催化剂中铑含量的方法
WO2024227909A1 (fr) * 2023-05-03 2024-11-07 Firmenich Sa Semi-hydrogénation sélective d'allène
CN118239990A (zh) * 2024-05-28 2024-06-25 北京元延医药科技股份有限公司 不对称氢化催化合成药物的稀有贵金属和手性膦的配合物
CN118239990B (zh) * 2024-05-28 2025-03-14 北京元延医药科技股份有限公司 不对称氢化催化合成药物的稀有贵金属和手性膦的配合物

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