Sn−Li Transmetalation of α‐Aminoorganostannanes for the Stereoselective Synthesis of Substituted Dehydropiperidines and Dehydroazepanes

A highly diastereoselective synthesis of (R,S) or (S,S) 2,6‐disubstituted dehydropiperidines and 2,7‐disubstituted dehydroazepanes has been developed. The stereochemical preference for the (R,S) or the (S,S) isomer is governed by a tin‐lithium exchange/electrophilic trapping sequence combined with a...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2019-08, Vol.361 (16), p.3777-3786
Main Authors: Lumbroso, Alexandre, Beaudet, Isabelle, Quintard, Jean‐Paul, Fraisse, Cécile, Galland, Nicolas, Toupet, Loïc, Le Grognec, Erwan
Format: Article
Language:English
Subjects:
Carbonyls
Chemical Sciences
Chiral carbanion
Dehydropiperidines
DFT calculations
Lithium
Metathesis
Organic chemistry
Physics
Ring-closing metathesis
Sn−Li exchange
Stereoselectivity
Synthesis
Tin
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Summary:A highly diastereoselective synthesis of (R,S) or (S,S) 2,6‐disubstituted dehydropiperidines and 2,7‐disubstituted dehydroazepanes has been developed. The stereochemical preference for the (R,S) or the (S,S) isomer is governed by a tin‐lithium exchange/electrophilic trapping sequence combined with a ring‐closing metathesis. Their relative order was found to have a dramatic influence on the interaction controlling the epimerization at the anionic center. In each case, the complete stereodivergence of the reactions sequence is explained by considering the stabilization brought by the lithium‐carbonyl coordination and rationalized by DFT calculations.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201900349