Enantioenriched α-Vinyl 1,4-Benzodiazepines and 1,4-Benzoxazepines via Enantioselective Rhodium-Catalyzed Hydrofunctionalizations of Alkynes and Allenes

被引：8
|
作者：
Velasco-Rubio, Alvaro [1 ]
Bernardez, Rodrigo [1 ]
Varela, Jesus A. [1 ]
Saa, Carlos [1 ]
机构：
[1] Univ Santiago de Compostela, Ctr Singular Invest Quim Biolox & Mat Mol, Dept Quim Organ, Santiago De Compostela 15782, Spain
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2021年 / 86卷 / 15期
关键词：
FORMAL TOTAL-SYNTHESIS; INTRAMOLECULAR HYDROAMINATION; TERMINAL OLEFINS; ONE-POT; TANDEM; HETEROCYCLES; ANNULATION; ISOCHROMANS; CYCLIZATION; ALLYLATION;
D O I：
10.1021/acs.joc.1c01268
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Benzofused seven-membered heterocycles such as 1,4-benzo[e]diazepines (1,4-BZDs) and 1,4-benzo[e]oxazepines (1,4-BZOs) were efficiently synthesized by Rh-catalyzed hydrofunctionalization of internal alkynes and allenes in good to excellent yields. The asymmetric hydroamination of (aminomethyl)anilines gave rise to 3-vinyl-1,4-BZDs with excellent enantioselectivities. Orthogonal N-deprotection of 1,4-BZDs allowed an easy entry to an advanced pyrrolobenzodiazepine metabolite of the V2-receptor antagonist Lixivaptan.
引用
收藏
页码：10889 / 10902
页数：14
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