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New Insights into the Chemistry of gem ‐Bis(phosphonates): Unexpected Rearrangement of Michael‐Type Acceptors
Author(s) -
Szajnman Sergio H.,
García Liñares Guadalupe,
Moro Pablo,
Rodriguez Juan B.
Publication year - 2005
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.200500097
Subject(s) - phosphonate , chemistry , nucleophile , electrophile , derivative (finance) , michael reaction , enol , stereochemistry , medicinal chemistry , organic chemistry , catalysis , financial economics , economics
The use of tetraethyl ethylidenebis(phosphonate) as a Michael acceptor with different nucleophiles was investigated. It was found that in some cases this compound undergoes phosphate removal, depending on the nature of the nucleophile. The chemical behavior of its epoxy derivative tetraethyl oxiranylidenebis(phosphonate) as an electrophile was also studied. This compound underwent a very attractive and remarkable phosphonate‐phosphate rearrangement resulting in the enol phosphate 8 regardless of the nucleophile employed. Different mechanistic studies were conducted in an attempt to explain the mechanisms involved. To the best of our knowledge, this reaction constitutes a remarkable novelty, being the first reported rearrangement reaction of an epoxy derivative of a gem ‐bis(phosphonate). In addition, evidence supporting the involvement of a radical or a polar mechanism, depending on the nature of the nucleophile, is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)