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A Novel Allyl Transfer Coupled with a Grob Fragmentation
Author(s) -
Li ShaoGang,
Chen HuiJun,
Yang YangYang,
Wu WenJu,
Wu Yikang
Publication year - 2015
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201500728
Subject(s) - carbocation , intramolecular force , fragmentation (computing) , aryl , chemistry , cope rearrangement , stereoselectivity , carroll rearrangement , stereochemistry , photochemistry , claisen rearrangement , organic chemistry , catalysis , alkyl , biology , ecology
A novel acid‐promoted rearrangement is disclosed. In the previously unknown transformation, an allyl group migrated to an in situ formed carbocation stabilized by an electron‐rich aryl or heteroaryl group, resulting in a stereoselective intramolecular Grob fragmentation. The outcome of the rearrangement observed with an array of substrates can be satisfactorily rationalized using a working hypothesis with the aid of a six‐membered transition state similar to those proposed for the anionic oxy‐Cope or oxonia‐Cope rearrangements, but involving only one instead of two double bonds.