C-アピカル O-エクアトリアルスピロホスホランにおける求電子性の増大：エクアトリアル平面上にある反結合性P-O結合の影響

山本 陽介; 松川 史郎; 秋葉 欣哉

doi:10.11494/kisoyuki.53.0.43.0

53rd Symposium on Organic Reactions

Session ID : P-19

DOI https://doi.org/10.11494/kisoyuki.53.0.43.0

Conference information

Co-host: The Chemical Society of Japan, The Chemical Society of Japan, Kyushu Branch, The Society of Synthetic Organic Chemistry, Japan (Cooperation)

Enhanced Electrophilicity of C-Apical O-Equatorial Spirophosphoranes: Effect of the σ*_P-O Orbital in the Equatorial Plane

*Yohsuke Yamamoto, Shiro Matsukawa, Kin-ya Akiba

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Keywords: O-cis spirophosphorane, σ^*_P-O orbital, α-carbanion, Wittig reaction, oxaphosphetane

CONFERENCE PROCEEDINGS FREE ACCESS

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Abstract

Reactionsa of the α-anion of anti-apicophilic C-apical O-equatorial spirophosphorane (O-cis) with electrophiles were examined. O-cis isomer reacted with PhCHO to form adducts instead of olefins, while Wittig type reaction took place to afford olefins quantitatively in the reaction of corresponding O-apical C-equatorial (O-trans) isomer. X-ray analysis of a hexacoordinate intermediate bearing an oxaphosphetane ring in the reaction of O-cis isomer was successful.

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