Transition State Analysis on Regioselectivity in Photocycloaddition Reactions of Cyclohexenone with Cycloalkenecarboxylates

DOI

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Other Title
  • 2‐シクロヘキセノン体とシクロアルケンカルボキシレートとの光付加環化反応における配向選択性の遷移状態解析

Description

The regioselectivities in [2+2]photocycloadditions of 2-cyclohexenone(1) to methyl cycloalkenecarboxylates(2-4) give drastic different experimental results depending on the ring size of the cycloalkenecarboxylates, that is to say that a gradual reversal of regioselectivity from head-to-head(hh) to head-to-tail(ht) adducts with the increasing ring size. We have located the roots of the regioselective difference by performing the frontier molecular orbital(FMO) and transition state(TS) analysis using MOPAC. We could explain that for methyl cyclobutenecarboxlate(2) TS energy differences of the second-step and back-reaction as well as the first-step has effects for the regioselectivities and for methyl cyclohexenecarboxylate(4) TS energy of the first-steps is the most important factor deciding the regioselectivities. In addition, We also report the results of the ab initio calculations in these TS geometrical optimizations.

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Details 詳細情報について

  • CRID
    1390282680713406080
  • NII Article ID
    130004575279
  • DOI
    10.11545/ciqs.toyoha.0.jp16.0
  • Data Source
    • JaLC
    • CiNii Articles
  • Abstract License Flag
    Disallowed

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