手性铜氢催化的利用不饱和羧酸作为醛替代物的对映选择性氢酰化反应。
Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates.
机构信息
Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
出版信息
J Am Chem Soc. 2017 Jun 21;139(24):8126-8129. doi: 10.1021/jacs.7b04937. Epub 2017 Jun 6.
Abstract
The direct asymmetric copper hydride (CuH)-catalyzed coupling of α,β-unsaturated carboxylic acids to aryl alkenes to access chiral α-aryl dialkyl ketones is reported. A variety of substrate substitution patterns, sensitive functional groups, and heterocycles are tolerated in this reaction, which significantly expands the range of accessible products compared with existing hydroacylation methodology. Although mechanistic studies are ongoing, we propose that CuH-catalyzed silylation of unsaturated acids occurs to access a uniquely effective acyl electrophilic coupling partner.
摘要
报告了一种直接不对称铜氢化物 (CuH) 催化的 α,β-不饱和羧酸与芳基烯烃的偶联反应，可获得手性 α-芳基二烷基酮。该反应对各种底物取代模式、敏感官能团和杂环具有耐受性，与现有的氢酰化方法相比，显著扩展了可获得产物的范围。虽然正在进行机理研究，但我们提出 CuH 催化的不饱和酸的硅烷化反应可获得一种独特有效的酰基亲电偶联体。
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1
Intermolecular Markovnikov-Selective Hydroacylation of Olefins Catalyzed by a Cationic Ruthenium-Hydride Complex.
ACS Catal. 2016 May 6;6(5):3336-3339. doi: 10.1021/acscatal.6b00856. Epub 2016 Apr 19.
2
Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles.
J Am Chem Soc. 2017 Feb 15;139(6):2192-2195. doi: 10.1021/jacs.6b13029. Epub 2017 Feb 1.
3
Cobalt-Catalyzed Enantio- and Diastereoselective Intramolecular Hydroacylation of Trisubstituted Alkenes.
Angew Chem Int Ed Engl. 2017 Feb 20;56(9):2449-2453. doi: 10.1002/anie.201611518. Epub 2017 Jan 24.
4
Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition.
Science. 2016 Oct 21;354(6310). doi: 10.1126/science.aah5133.
5
Asymmetric Induction in Hydroacylation by Cooperative Iminium Ion-Transition-Metal Catalysis.
Org Lett. 2016 Nov 4;18(21):5588-5591. doi: 10.1021/acs.orglett.6b02825. Epub 2016 Oct 21.
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
Copper-Catalyzed Enantioselective Addition of Styrene-Derived Nucleophiles to Imines Enabled by Ligand-Controlled Chemoselective Hydrocupration.
J Am Chem Soc. 2016 Aug 10;138(31):9787-90. doi: 10.1021/jacs.6b06299. Epub 2016 Aug 1.
8
Chiral Integrated Catalysts Composed of Bifunctional Thiourea and Arylboronic Acid: Asymmetric Aza-Michael Addition of α,β-Unsaturated Carboxylic Acids.
Chem Pharm Bull (Tokyo). 2016;64(7):704-17. doi: 10.1248/cpb.c15-00983.
9
Asymmetric Hydroarylation of Vinylarenes Using a Synergistic Combination of CuH and Pd Catalysis.
J Am Chem Soc. 2016 Jul 13;138(27):8372-5. doi: 10.1021/jacs.6b04566. Epub 2016 Jul 1.
10
Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones.
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