Computationally Designed Dearomative Claisen-Type Rearrangement of a Benzyl Alkynyl Ether and Cascade Reaction To
Keisuke Fukaya1, Kaoru Tanaka1, Ryo Karashimada1
1Biotechnology Research Center and Department of Biotechnology, Toyama Prefectural University, 5180 Kurokawa, Imizu, Toyama 939-0398, Japan.
Abstract:
Computer-aided substrate design is an effective approach to developing new reactions. Here, we report the dearomative Claisen-type rearrangement along with the construction of a quaternary carbon via comprehensive evaluation of the transition states of virtual substrates. The experimental rearrangement of 2,4,6-trimethyl benzyl alkynyl ether occurs as designed. Serendipitously, the rearrangement is followed by cyclization to the 3/4/6-tricyclic system and opening of the four-membered ring accompanied by methyl group migration to afford a dihydroindenone derivative.
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