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Metalated Epoxides as Carbenoids − Further Advances in the Stereospecific Synthesis of Spirocyclopropanes
Author(s) -
Dechoux Luc,
Agami Claude,
Doris Eric,
Mioskowski Charles
Publication year - 2001
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 - 10.1002/1099-0690(200111)2001:21<4107::aid-ejoc4107>3.0.co;2-a
Subject(s) - cyclopropanation , chemistry , stereospecificity , intramolecular force , nucleophile , stereochemistry , ring (chemistry) , hydrolysis , cyclopropane , organic chemistry , catalysis
The intramolecular cyclopropanation of β,γ‐unsaturated metalated epoxides derived from 11 yielded the highly strained tricyclic intermediates 7 . The facile hydrolysis of the latter species afforded the α‐keto spirocyclopropanes 8 in a stereospecific fashion. Indeed, the stereochemistry of the starting alkenes 11d − e governs the relative configuration of the cyclopropanes 8d − e . Furthermore, these spiro systems readily underwent acid‐mediated ring opening by various nucleophiles, leading to the substituted enones 12 .