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Acceleration of Inward Ring Opening of 3‐Phosphorylcyclobutenes
Author(s) -
Ishida Naoki,
Yano Takaaki,
Murakami Masahiro
Publication year - 2017
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201600585
Subject(s) - cyclobutene , chemistry , ring (chemistry) , atomic orbital , phosphonate , computational chemistry , stereochemistry , crystallography , photochemistry , organic chemistry , quantum mechanics , physics , electron
Abstract 3‐Phosphorylcyclobutenes undergo a 4π‐electrocyclic ring opening reaction faster than cyclobutene itself, and afford the corresponding 1,3‐dienes with the cis isomer predominating. The accelerating effect and the inward preference of the phosphonate substituents are ascribed to the orbital interaction between the breaking C−C σ‐orbital of the cyclobutene backbone with the P−O σ* orbitals at the transition state.