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

被引：41
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
收藏
页码：6940 / 6945
页数：6
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