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1,2‐Silyl‐migrative cyclization of vinylsilanes bearing an amino group
Author(s) -
Miura Katsukiyo,
Takahashi Tatsuyuki,
Hondo Takeshi,
Hosomi Akira
Publication year - 2002
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.10150
Subject(s) - chemistry , silylation , vinylsilane , alkyl , methylene , stereospecificity , catalysis , selectivity , medicinal chemistry , bearing (navigation) , group (periodic table) , stereochemistry , organic chemistry , cartography , geography
In the presence of an acid catalyst, α‐alkyl‐substituted ( Z )‐vinylsilanes 1, bearing a tosylamino group, were smoothly cyclized to trans ‐2‐alkyl‐3‐silylpiperidines 2 (1,2‐silyl‐migration products) and (2 R *, 1′ S *)‐2‐(1′‐silylalkyl)pyrrolidines 3 . The elaboration of the reaction conditions enabled the selective preparation of each cyclized product. The acid‐catalyzed cyclization of ( Z )‐vinylsilane 5, whose methylene tether is shorter than that of 1 by one carbon, formed only the 1,2‐silyl‐migration product 6 with high trans ‐selectivity. These cyclizations were found to proceed in a stereospecific manner. Chirality 15:41–52, 2003. © 2002 Wiley‐Liss, Inc.