CuH 催化的 α,β-不饱和羧酸的不对称还原反应生成β-手性醛。
CuH-Catalyzed Asymmetric Reduction of α,β-Unsaturated Carboxylic Acids to β-Chiral Aldehydes.
机构信息
Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
出版信息
J Am Chem Soc. 2018 Jan 17;140(2):606-609. doi: 10.1021/jacs.7b12260. Epub 2018 Jan 4.
Abstract
The copper hydride (CuH)-catalyzed enantioselective reduction of α,β-unsaturated carboxylic acids to saturated aldehydes is reported. This protocol provides a new method to access a variety of β-chiral aldehydes in good yields, with high levels of enantioselectivity and broad functional group tolerance. A reaction pathway involving a ketene intermediate is proposed based on preliminary mechanistic studies and density functional theory calculations.
摘要
报道了铜氢化物（CuH）催化的α，β-不饱和羧酸对映选择性还原为饱和醛。该方案为获得各种β-手性醛提供了一种新方法，产率高，对映选择性高，官能团容忍度广。基于初步的机理研究和密度泛函理论计算，提出了一种涉及烯酮中间体的反应途径。
相似文献
1
CuH-Catalyzed Asymmetric Reduction of α,β-Unsaturated Carboxylic Acids to β-Chiral Aldehydes.
J Am Chem Soc. 2018 Jan 17;140(2):606-609. doi: 10.1021/jacs.7b12260. Epub 2018 Jan 4.
2
Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates.
J Am Chem Soc. 2017 Jun 21;139(24):8126-8129. doi: 10.1021/jacs.7b04937. Epub 2017 Jun 6.
3
CuH-Catalyzed Asymmetric Reductive Amidation of α,β-Unsaturated Carboxylic Acids.
Org Lett. 2020 Jul 17;22(14):5666-5670. doi: 10.1021/acs.orglett.0c02064. Epub 2020 Jul 6.
4
Catalytic enantioselective difluoroalkylation of aldehydes.
Angew Chem Int Ed Engl. 2013 Jul 22;52(30):7869-73. doi: 10.1002/anie.201303551. Epub 2013 Jun 18.
5
CuH-Catalyzed Regio- and Enantioselective Hydrocarboxylation of Allenes: Toward Carboxylic Acids with Acyclic Quaternary Centers.
J Am Chem Soc. 2021 Apr 7;143(13):4935-4941. doi: 10.1021/jacs.1c01880. Epub 2021 Mar 24.
6
Enantioselective synthesis of beta-aryl-gamma-amino acid derivatives via Cu-catalyzed asymmetric 1,4-reductions of gamma-phthalimido-substituted alpha,beta-unsaturated carboxylic acid esters.
J Org Chem. 2008 Aug 1;73(15):6022-4. doi: 10.1021/jo800794p. Epub 2008 Jul 3.
7
Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids.
J Am Chem Soc. 2016 May 11;138(18):5821-4. doi: 10.1021/jacs.6b03086. Epub 2016 Apr 29.
8
Chiral diphosphine and monodentate phosphorus ligands on a spiro scaffold for transition-metal-catalyzed asymmetric reactions.
Acc Chem Res. 2008 May;41(5):581-93. doi: 10.1021/ar700137z. Epub 2008 Mar 1.
9
Copper-Catalyzed Enantioselective Reductive Aldol Reaction of α,β-Unsaturated Carboxylic Acids to Alkyl Aryl Ketones: Silanes as Activator and Transient Protecting Group.
Chemistry. 2022 Feb 16;28(9):e202104273. doi: 10.1002/chem.202104273. Epub 2022 Jan 21.
10
An organocatalytic Michael-cyclization cascade of 4-oxa-α,β-unsaturated carboxylic acids with aldehydes: facile synthesis of chiral γ-lactols and trisubstituted γ-lactones.
Chem Commun (Camb). 2015 Feb 28;51(17):3596-9. doi: 10.1039/c4cc09686j.
引用本文的文献
1
Iridium-Catalyzed Highly Selective 1,4-Reduction of α,β-Unsaturated Carbonyl Compounds.
Molecules. 2024 Dec 14;29(24):5912. doi: 10.3390/molecules29245912.
2
Kinetic Resolution of β-Branched Aldehydes through Peptide-Catalyzed Conjugate Addition Reactions.
J Am Chem Soc. 2024 Jul 17;146(28):19101-19107. doi: 10.1021/jacs.4c03617. Epub 2024 Jul 3.
3
CuH-Catalyzed Selective N-Methylation of Amines Using Paraformaldehyde as a C1 Source.
ACS Omega. 2023 Aug 9;8(33):30640-30645. doi: 10.1021/acsomega.3c04332. eCollection 2023 Aug 22.
4
Metal-Free Hydrosilylation of Ketenes with Silicon Electrophiles: Access to Fully Substituted Aldehyde-Derived Silyl Enol Ethers.
Chemistry. 2021 Jun 4;27(32):8273-8276. doi: 10.1002/chem.202100877. Epub 2021 May 6.
5
CuH-Catalyzed Asymmetric Reductive Amidation of α,β-Unsaturated Carboxylic Acids.
Org Lett. 2020 Jul 17;22(14):5666-5670. doi: 10.1021/acs.orglett.0c02064. Epub 2020 Jul 6.
6
CuH-Catalyzed Olefin Functionalization: From Hydroamination to Carbonyl Addition.
Acc Chem Res. 2020 Jun 16;53(6):1229-1243. doi: 10.1021/acs.accounts.0c00164. Epub 2020 May 13.
7
Catalytic enantioselective addition of organometallics to unprotected carboxylic acids.
Nat Commun. 2019 Jul 30;10(1):3402. doi: 10.1038/s41467-019-11345-z.
8
Atomically Precise, Thiolated Copper-Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions.
ACS Nano. 2019 May 28;13(5):5975-5986. doi: 10.1021/acsnano.9b02052. Epub 2019 May 10.
9
Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes.
J Am Chem Soc. 2018 Feb 7;140(5):1627-1631. doi: 10.1021/jacs.8b00643. Epub 2018 Jan 29.
本文引用的文献
1
Mechanism-based enhancement of scope and enantioselectivity for reactions involving a copper-substituted stereogenic carbon centre.
Nat Chem. 2018 Jan;10(1):99-108. doi: 10.1038/nchem.2861. Epub 2017 Oct 2.
2
Mechanistic Studies of Copper-Catalyzed Asymmetric Hydroboration of Alkenes.
J Am Chem Soc. 2017 Sep 13;139(36):12758-12772. doi: 10.1021/jacs.7b07124. Epub 2017 Sep 1.
3
Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates.
J Am Chem Soc. 2017 Jun 21;139(24):8126-8129. doi: 10.1021/jacs.7b04937. Epub 2017 Jun 6.
4
Recent advances in organocatalytic enantioselective transfer hydrogenation.
Org Biomol Chem. 2017 Mar 21;15(11):2307-2340. doi: 10.1039/c7ob00113d. Epub 2017 Feb 23.
5
Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition.
Science. 2016 Oct 21;354(6310). doi: 10.1126/science.aah5133.
6
Balancing C=C Functionalization and C=O Reduction in Cu-H Catalysis.
Angew Chem Int Ed Engl. 2016 Sep 26;55(40):12148-9. doi: 10.1002/anie.201606701. Epub 2016 Aug 4.
7
Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity.
Chem Rev. 2016 Aug 10;116(15):8318-72. doi: 10.1021/acs.chemrev.6b00366. Epub 2016 Jul 25.
8
Iridium-Catalyzed Selective Isomerization of Primary Allylic Alcohols.
Acc Chem Res. 2016 Jun 21;49(6):1232-41. doi: 10.1021/acs.accounts.6b00144. Epub 2016 May 9.
9
CuH-Catalysed Hydroamination of Styrene with Hydroxylamine Esters: A Coupled Cluster Scrutiny of Mechanistic Pathways.
Chemistry. 2016 Jun 6;22(24):8290-300. doi: 10.1002/chem.201600230. Epub 2016 May 3.
10
Copper-catalysed enantioselective stereodivergent synthesis of amino alcohols.
Nature. 2016 Apr 21;532(7599):353-6. doi: 10.1038/nature17191. Epub 2016 Mar 28.
Zotero 插件