Reactive Intermediates Produced in the Decomposition of 2-Diazoketone : Mechanism of the Wolff Rearrangement(Physicla,Chemical)

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Potential energy hypersurfaces of the nitrogen elimination and the Wolff rearrangement were investigated for both cyclic and open-chain 2-diazoketanes by means of semi-empirical MINDO/3 molecular orbital calculations with configuration intcraction. In the case of 2-diazobenzen-1-one, the nitrogen elimination takes place simultaneously with the Wolff rearrangement in a concerted fashion and neither ketocarbene nor oxirene is produced. In contrast to the cyciic 2-diazoketone. 2-diazoethan-1-one produces oxirene through nitrogen elimination in a concerted fashion. The oxirene isomerizes to ketene via the Wolff rearrangement, passing over a second saddle point of low energy. No ketocarbene intermediate is produced in either case.
公益社団法人日本薬学会の論文
1987-01-25