Copper-Catalyzed Enantioselective Formation of C-CF3 Centers from β-CF3-Substituted Acrylates and Acrylonitriles

被引：15

作者：

Poutrel, Pauline ^{[1
]}

Ivanova, Maria V. ^{[1
]}

Pannecoucke, Xavier ^{[1
]}

Jubault, Philippe ^{[1
]}

Poisson, Thomas ^{[1
,2
]}

机构：

[1] Normandie Univ, INSA Rouen, UNIROUEN, CNRS,COBRA,UMR 6014, F-76000 Rouen, France

[2] Inst Univ France, 1 Rue Descartes, F-75231 Paris, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2019年 / 25卷 / 67期

关键词：

asymmetric catalysis; copper; hydrides; reduction; trifluoromethyl group; CONJUGATE ADDITION; MICHAEL ADDITION; ALLYLIC TRIFLUOROMETHYLATION; ALPHA-TRIFLUOROMETHYLATION; FLUORINATION; PERFLUOROALKYLATION; HYDROGENATION; REACTIVITY; REDUCTION; EFFICIENT;

D O I：

10.1002/chem.201904192

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The catalytic asymmetric synthesis of beta-trifluoromethylated esters or nitriles is reported. The use of an in situ formed chiral Cu-H complex allowed the enantioselective reduction of beta-trifluoromethylated acrylates or acrylonitriles. The reaction proceeds smoothly affording the corresponding enantioenriched products in good to excellent yields and outstanding enantioselectivities (up to 98 % ee). The mechanism of the reaction was studied, and a plausible reaction pathway was suggested accordingly. Finally, the versatility of the products was highlighted through functional group manipulations.

引用

页码：15262 / 15266

页数：5

共 69 条

[1] The Productive Merger of Iodonium Salts and Organocatalysis: A Non-photolytic Approach to the Enantioselective α-Trifluoromethylation of Aldehydes [J].

Allen, Anna E. ;

MacMillan, David W. C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (14) :4986-+

[2] Selective Copper Complex-Catalyzed Hydrodefluorination of Fluoroalkenes and Allyl Fluorides: A Tale of Two Mechanisms [J].

Andrella, Nicholas O. ;

Xu, Nancy ;

Gabidullin, Bulat M. ;

Ehm, Christian ;

Baker, R. Tom .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2019, 141 (29) :11506-11521

[3]

[Anonymous], 2011, ANGEW CHEM

[4] Asymmetric conjugate reduction of α,β-unsaturated esters using a chiral phosphine-copper catalyst [J].

Appella, DH ;

Moritani, Y ;

Shintani, R ;

Ferreira, EM ;

Buchwald, SL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (40) :9473-9474

[5] Copper-Catalyzed Innate Ethoxycarbonyldifluoromethylation of Electron-Rich Arenes [J].

Belhomme, Marie-Charlotte ;

Bayle, Alexandre ;

Poisson, Thomas ;

Pannecoucke, Xavier .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2015, 2015 (08) :1719-1726

[6] Copper-Catalyzed Direct C-2 Difluoromethylation of Furans and Benzofurans: Access to C-2 CF2H Derivatives [J].

Belhomme, Marie-Charlotte ;

Poisson, Thomas ;

Pannecoucke, Xavier .

JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (15) :7205-7211

[7] Copper Catalyzed β-Difluoroacetylation of Dihydropyrans and Glycals by Means of Direct C-H Functionalization [J].

Belhomme, Marie-Charlotte ;

Poisson, Thomas ;

Pannecoucke, Xavier .

ORGANIC LETTERS, 2013, 15 (13) :3428-3431

[8] 1,4-Addition of the CF3 group, perfluoroalkyl groups and functionalized difluoromethylated moieties: An overview [J].

Besset, Tatiana ;

Poisson, Thomas ;

Pannecoucke, Xavier .

JOURNAL OF FLUORINE CHEMISTRY, 2015, 178 :225-240

[9] Recent Progress in Direct Introduction of Fluorinated Groups on Alkenes and Alkynes by means of C-H Bond Functionalization [J].

Besset, Tatiana ;

Poisson, Thomas ;

Pannecoucke, Xavier .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (51) :16830-16845

[10] Synthesis of Functionalized Indoles with a Trifluoromethyl-Substituted Stereogenic Tertiary Carbon Atom Through an Enantioselective Friedel-Crafts Alkylation with β-Trifluoromethyl-α,β-enones [J].

Blay, Gonzalo ;

Fernandez, Isabel ;

Carmen Munoz, M. ;

Pedro, Jose R. ;

Vila, Carlos .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (30) :9117-9122

← 1 2 3 4 5 6 7 →