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Evidence of Formation of an exo ‐π‐Allyl Complex Intermediate in the Pd 0 ‐Catalyzed Alkylation of a Bicyclic Allylic Diacetate with Stabilized Carbon Nucleophiles
Author(s) -
Brunel Jean Michel,
Maffei Michel,
Muchow Günter,
Buono Gérard
Publication year - 2000
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/(sici)1099-0690(200005)2000:9<1799::aid-ejoc1799>3.0.co;2-b
Subject(s) - chemistry , nucleophile , bicyclic molecule , catalysis , tsuji–trost reaction , alkylation , allylic rearrangement , medicinal chemistry , organic chemistry
Abstract The palladium(0)‐catalyzed alkylation of 2,3‐bis(acetoxymethyl)bicyclo[2.2.1]hepta‐2,5‐diene 1 with malonate‐type enolates as nucleophiles is investigated. A monoalkylated product is formed first, and undergoes (depending on the nucleophile used) a second intramolecular reaction leading to spirocyclopropane‐annulated bicyclo[2.2.1]heptene derivatives 5 . The formation of endo spirobicyclic cyclopropanes adducts as major isomer is rationalized by assuming formation of an intermediate exo ‐(π‐allyl)palladium complex.

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