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Novel Transformations of 1,2‐Dioxetanes: β‐Hydroxy Ethers by Addition of Alkyllithium Reagents
Author(s) -
Adam Waldemar,
Heil Markus
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250137
Subject(s) - chemistry , reactivity (psychology) , epoxide , acetophenone , nucleophile , reagent , dioxetane , nucleophilic addition , medicinal chemistry , photochemistry , halogen , organic chemistry , chemiluminescence , catalysis , medicine , alternative medicine , pathology , alkyl
The reaction of 1,2‐dioxetanes with alkyllithium reagents was investigated. The 3,3‐disubstituted dioxetanes 2a , d and their halogen‐substituted analogues 2b , c , which were used as probes to differentiate between the mechanistic alternatives (S N 2 reactivity vs. single‐electron transfer), reacted with n ‐BuLi to afford the β‐hydroxy ethers 3a — d . Additionally, the epoxide 4 was obtained from dioxetanes 2b , c . The epoxide 5 and a small amount of acetophenone were found in the reaction of dioxetane 2c with triphenylmethyllithium, but only the minor part of the dioxetane‐derived products could be identified. The observation of the epoxides 4 and 5 led to the mechanistic conclusion that nucleophilic attack (S N 2 reactivity) is the most prominent process in this reaction.