Catalytic Enantioselective Conjugate Alkynylation of α,β-Unsaturated 1,1,1-Trifluoromethyl Ketones with Terminal Alkynes

被引:16
|
作者
Sanz-Marco, Amparo [1 ]
Blay, Gonzalo [1 ]
Carmen Munoz, M. [2 ]
Pedro, Jose R. [1 ]
机构
[1] Univ Valencia, Fac Quim, Dept Quim Organ, C Dr Moliner 50, Burjasso 46100, Spain
[2] Univ Politecn Valencia, Dept Fis Aplicada, Cami Vera S-N, E-46022 Valencia, Spain
关键词
alkynes; asymmetric catalysis; conjugate addition; enones; fluorine; TRIFLUOROMETHYL KETONES; MEDICINAL CHEMISTRY; ASYMMETRIC-SYNTHESIS; PHOSPHOLIPASE A(2); CARBONYL-COMPOUNDS; FLUORINE; ORGANOCUPRATE; 1,3-DIYNES; INHIBITORS; REACTIVITY;
D O I
10.1002/chem.201601303
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The first catalytic enantioselective conjugate alkynylation of alpha,beta-unsaturated 1,1,1-trifluoromethyl ketones has been carried out. Terminal alkynes and 1,3-diynes were treated with trifluoromethyl ketones in the presence of a low catalytic load of a Cu-I-MeOBIPHEP complex (2.5 mol%) and triethylamine (10 mol%) to give the corresponding trifluoromethyl ketones bearing a propargylic stereogenic center at the beta position with good yields and excellent enantiomeric excesses in most of the cases. No 1,2-addition products were formed under the reaction conditions. The procedure showed broad substrate scope for alkyne, diyne, and enone. A rationale for the observed stereochemistry has been provided. Finally, the potential application of the reaction products in the synthesis of chiral tetrahydrofurans bearing a trifluoromethylated quaternary stereocenter has been devised.
引用
收藏
页码:10057 / 10064
页数:8
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