Semipinacol Rearrangement Induced by Cleavage of Dibromocyclopropane

A novel semipinacol rearrangement using dibromocyclopropanes as sources of carbocations was developed. Heating dibromocyclopropanes bearing a 1‐hydroxyalkyl group with silver perchlorate and 2,6‐lutidine induced cleavage of the cyclopropane ring to form allyl cations, which underwent 1,2‐shift of a...

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Published inEuropean journal of organic chemistry Vol. 2020; no. 27; pp. 4108 - 4111
Main Authors Kurimoto, Michitaka, Nakajima, Daisuke, Nishiyama, Yoshitake, Yokoshima, Satoshi
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 23.07.2020
Wiley Subscription Services, Inc
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Summary:A novel semipinacol rearrangement using dibromocyclopropanes as sources of carbocations was developed. Heating dibromocyclopropanes bearing a 1‐hydroxyalkyl group with silver perchlorate and 2,6‐lutidine induced cleavage of the cyclopropane ring to form allyl cations, which underwent 1,2‐shift of a substituent at the α‐position of the hydroxy group to give β,γ‐unsaturated carbonyl compounds having a quaternary carbon at the α‐position. Because the products have convertible functional groups such as bromo, vinyl, and formyl groups, the method is expected to be applicable to the synthesis of various molecules. A novel semipinacol rearrangement using dibromocyclopropanes as sources of carbocations was developed. Heating dibromocyclopropanes bearing a 1‐hydroxyalkyl group with silver perchlorate and 2,6‐lutidine induced cleavage of the cyclopropane ring to form allyl cations, which underwent 1,2‐shift of a substituent at the α‐position of the hydroxy group to give β,γ‐unsaturated carbonyl compounds having a quaternary carbon at the α‐position.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202000355