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Stereodivergent Synthesis of N‐Heterocycles by Catalyst‐Controlled, Activity‐Directed Tandem Annulation of Diazo Compounds with Amino Alkynes
Author(s) -
Liu Kai,
Zhu Chenghao,
Min Junxiang,
Peng Shiyong,
Xu Guangyang,
Sun Jiangtao
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201507122
Subject(s) - carbenoid , annulation , diazo , hydroamination , chemistry , tandem , intramolecular force , catalysis , combinatorial chemistry , rhodium , methylene , cyclopropanation , stereochemistry , medicinal chemistry , organic chemistry , materials science , composite material
A stereodivergent synthesis of five‐membered N‐heterocycles, such as 2,3‐dihydropyrroles, and 2‐methylene and 3‐methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper‐catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium‐catalyzed protocol features a carbenoid insertion into the NH bond and subsequent Conia‐ene cyclization.