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Sn−Li Transmetalation of α‐Aminoorganostannanes for the Stereoselective Synthesis of Substituted Dehydropiperidines and Dehydroazepanes
Author(s) -
Lumbroso Alexandre,
Beaudet Isabelle,
Quintard JeanPaul,
Fraisse Cécile,
Galland Nicolas,
Toupet Loïc,
Le Grognec Erwan
Publication year - 2019
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201900349
Subject(s) - transmetalation , chemistry , electrophile , stereoselectivity , lithium (medication) , epimer , stereochemistry , metathesis , sequence (biology) , tin , ring closing metathesis , medicinal chemistry , computational chemistry , organic chemistry , catalysis , polymerization , medicine , biochemistry , polymer , endocrinology
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.