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Synthesis and Properties of Functionalized 2,4‐Ethano‐Bridged Bicyclobutanes
Author(s) -
Hogeveen H.,
Zwart L.
Publication year - 1981
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198100042
Subject(s) - chemistry , dichlorocarbene , cyclopropane , allene , ozonolysis , ketone , steric effects , alkene , double bond , adduct , medicinal chemistry , photochemistry , alkyl , hexane , stereochemistry , organic chemistry , ring (chemistry) , catalysis
Starting from 1,2,4,5,6‐pentamethyl‐3‐methylenetricyclo[3.1.0.0 2.6 ]‐ hexane ( 3 ), a number of functionalized ethano‐bridged bicyclobutanes have been prepared. Ozonolysis of the carbon‐carbon double bond of compound 3 leads to the strained and sterically hindered ketone 4 which can be further transformed into tricyclic alcohols and azines. The formation of the rearranged lactone 19 in the oxidation of ketone 4 with O 3 or peracid is in agreement with a mechanism in which the 1,2‐alkyl shift from carbon to oxygen occurs by way of a β‐fission followed by a recombination step. Treatment of the dichlorocarbene adduct of alkene 3 with n‐BuLi afforded allene 7 , which on reaction with TCNE yielded a di‐ cis ‐fused cyclopropane.