捻れた 1, 3-ジエンが示すユニークな反応性

概要

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We have recently found the novel character of twisted 1, 3-dienes in two types of reactions; one is photosensitized oxygenation and another is anion formation with base. In the former reaction, the selective allene formation resulting from the ene reaction of the vinyl hydrogen rather than the allyl hydrogen was disclosed. On the basis of MM and MO calculations, the abnormally higher reactivity of the vinyl hydrogen would be rationalized by considering the σ-π orbital interaction between the vinyl C-H bond and another double bond. Diastereoselective allene formation resulting from the chiral projection from sp<SUP>3</SUP> carbon into an allene was also realized. In the latter reaction, the selective vinyl anion formation rather than benzylic anion formation was observed in the twisted styrene derivatives. In this paper, we will describe our recent study on twisted 1, 3-dienes in detail, in addition to the recent topics by another research groups.
社団法人有機合成化学協会の論文
2003-09-01