Catalytic Asymmetric Umpolung Allylation/2-Aza-Cope Rearrangement for the Construction of α-Tetrasubstituted α-Trifluoromethyl Homoallylic Amines

被引：43

作者：

Shen, Chong ^{[1
]}

Wang, Ruo-Qing ^{[1
]}

Wei, Liang ^{[1
]}

Wang, Zuo-Fei ^{[1
]}

Tao, Hai-Yan ^{[1
]}

Wang, Chun-Jiang ^{[1
,2
]}

机构：

[1] Wuhan Univ, Engn Res Ctr Organosilicon Cpds & Mat, Minist Educ, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China

[2] Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 17期

基金：

中国博士后科学基金;

关键词：

ALLYLIC ALKYLATION; ENANTIOSELECTIVE SYNTHESIS; TRANSFER HYDROGENATION; NUCLEOPHILIC TRIFLUOROMETHYLATION; EFFICIENT SYNTHESIS; COPE REARRANGEMENT; IMINES; ALLYLATION; REAGENTS; FLUORINE;

D O I：

10.1021/acs.orglett.9b02543

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A general protocol for the preparation of enantioenriched alpha-tetrasubstituted alpha-trifluoromethyl homoallylic amines is disclosed. Despite the significant challenge in stereoselectivity control, Ir-catalyzed asymmetric cascade umpolung allylation/2-aza-Cope rearrangement of trifluoromethylated fluorenone imines with allylic carbonates was realized with excellent efficiency and remarkable stereoselectivity. These were enabled by the suitable protective imino moiety and an unexpectedly exclusive E-geometrical imine of the allylation intermediate. This methodology is also applicable to facile access to chiral alpha-trisubstituted alpha-trifluoromethyl homoallylic amines in similarly high yield and stereoselectivity.

引用

页码：6940 / 6945

页数：6

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