Direct Conversion of N-Alkylamines to N-Propargylamines through C-H Activation Promoted by Lewis Acid/Organocopper Catalysis: Application to Late-Stage Functionalization of Bioactive Molecules

被引:46
作者
Chan, Jessica Z. [1 ]
Yesilcimen, Ahmet [1 ]
Cao, Min [1 ]
Zhang, Yuyang [1 ]
Zhang, Bochao [1 ]
Wasa, Masayuki [1 ]
机构
[1] Boston Coll, Merkert Chem Ctr, Dept Chem, Chestnut Hill, MA 02467 USA
关键词
ASYMMETRIC ALKYNYLATION; ENANTIOSELECTIVE ALKYNYLATION; TERMINAL ALKYNES; DIRECT-ADDITION; B(C6F5)(3); HYDROSILYLATION; IMINES; PAIRS; ARYL; TETRAHYDROISOQUINOLINES;
D O I
10.1021/jacs.0c08599
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An efficient catalytic method to convert an alpha-C-H bond of N-alkylamines into an alpha-C-alkynyl bond was developed. In the past, such transformations were carried out under oxidative conditions, and the enantioselective variants were confined to tetrahydroisoquinoline derivatives. Here, we disclose a method for the union of N-alkylamines and trimethylsilyl alkynes, without the presence of an external oxidant and promoted through cooperative actions of two Lewis acids, B(C6F5)(3) and a Cu-based complex. A variety of propargylamines can be synthesized in high diastereo- and enantioselectivity. The utility of the approach is demonstrated by the late-stage site-selective modification of bioactive amines. Kinetic investigations that shed light on various mechanistic nuances of the catalytic process are presented.
引用
收藏
页码:16493 / 16505
页数:13
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