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Thermal and hyperbaric addition of N,N ‐ and N,O ‐ binucleophiles on cycloalkylidenic bromo esters
Author(s) -
Rulev Alexandre Y.,
Maddaluno Jacques
Publication year - 2002
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.493
Subject(s) - chemistry , allylic rearrangement , halogen , double bond , medicinal chemistry , primary (astronomy) , cascade , stereochemistry , organic chemistry , alkyl , catalysis , physics , chromatography , astronomy
Abstract The thermal and high‐pressure (11 kbar) induced reaction between 2‐bromo‐2‐(cycloalkylidene)acetates and N,O ‐ and N,N ‐binucleophiles (such as ethylenediamines or aminoethanols) provides morpholin‐2‐ones and piperazin‐2‐ones. Thus, in contrast to simple primary amines, binucleophiles do not form spirocyclic derivatives. The expected Michael addition competes with a cascade reaction consisting of a migration of the double bond followed by the substitution of the newly established allylic halogen and a lactonization (lactamization), and eventually ended by a back‐migration of the double bond. Copyright © 2002 John Wiley & Sons, Ltd.