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Mechanism and origin of stereoselectivity in Robinson annulations leading to bicyclo[3.3.1]nonanes: a rare Curtin–Hammet scenario
Author(s) -
Wang Dong,
Miao Longfei,
Feng Lixia,
Yao Qingwei,
Mkrtchyan Gnel,
Crowe William E.,
Nesterov Evgueni E.,
Wang Yuekui,
Zhang Xiaoting,
Yu Peng
Publication year - 2017
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3595
Subject(s) - chemistry , diastereomer , bicyclic molecule , annulation , stereoselectivity , mechanism (biology) , stereochemistry , catalysis , organic chemistry , philosophy , epistemology
Computational studies on the mechanism and diastereoselectivity of base catalyzed synthesis of bicyclo[3.3.1]nonanes by Robinson annulation are reported. Three possible mechanisms were considered, and only the methanol assisted H‐shift process could be the favorable pathway. We have discovered a rare Curtin–Hammet scenario: rate determining steps for the two diastereomeric products formed are completely different reactions, and a correction factor should be considered when gauging the ratio of products from competing pathways. The pathway leading to the anti product is kinetically preferred, which is consistent with experimental results. Finally, the ratio of the two products was rationalized. Copyright © 2016 John Wiley & Sons, Ltd.