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A Route to 2‐Alkenyl‐3‐( tert ‐butyldiphenylsilyl)amines and Application to the Construction of a Tricyclic Ring System
Author(s) -
Yadav Veejendra K.,
Narhe Bharat D.,
Kumar Kamlesh,
Hulikal Vijaykumar
Publication year - 2013
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201300319
Subject(s) - tosyl , chemistry , deprotonation , cleavage (geology) , ring (chemistry) , bond cleavage , ion , medicinal chemistry , carbenium ion , stereochemistry , organic chemistry , catalysis , geotechnical engineering , fracture (geology) , engineering
Abstract N ‐ Tosyl 3,3 ‐ dialkyl ‐ 2 ‐ ( tert ‐ butyldiphenylsilylmethyl)azetidines rearrange smoothly into the corresponding 2 ‐ alkenyl ‐ 3 ‐ ( tert ‐ butyldiphenylsilyl)amines upon exposure to BF 3 · OEt 2 in CH 2 Cl 2 . The reaction involves sequential σ C–N bond cleavage, 1,2 ‐ migration of the N ‐ tosyl‐aminomethyl group, and deprotonation of the resultant tert ‐ carbenium ions. For the instance in which the carbenium ion formed from migration of the N ‐ tosyl‐aminomethyl group is highly stable by virtue of being, for example, tertiary as well as benzylic, the migration takes place in sync with σ C–N bond cleavage, which leads to high configurational control at the tert ‐butyldiphenylsilylmethyl ‐ bearing carbon atom in the product.