Ab initio MO study on [3 + 2] annulation using β-phenylthio-acryloylsilanes with alkyl methyl ketone enolates and its through-space/bond interaction analysis

Yuuichi Orimoto, Kazunari Naka, Kei Takeda, Yuriko Aoki

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Ab initio through-space/bond interaction analysis was applied to [3 + 2] annulation based on Brook rearrangement using β-phenylthio-acryloylsilanes with alkyl methyl ketone enolates. An uncertain reaction mechanism, wherein a bulky cyclopentenol with large substituents on the same side of the five-membered ring was obtained as a major product, can be explained by the low activation energy of its reaction pathway. Intramolecular orbital interactions related to the carbanion generated by Brook rearrangement preferentially provide the stabilization of the reaction pathway to the bulky cyclopentenol (major product) compared with that provided to the non-bulky cyclopentenol (minor product). In addition, ab initio molecular orbital calculations suggest the existence of an E/Z conformational inversion after Brook rearrangement. This result accurately explains the loss of the E/Z stereochemical integrity in the starting materials of the experiment.

Original languageEnglish
Pages (from-to)2244-2249
Number of pages6
JournalOrganic and Biomolecular Chemistry
Volume3
Issue number12
DOIs
Publication statusPublished - Jun 21 2005

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Orbital calculations
Molecular orbitals
Ketones
ketones
Stabilization
Activation energy
products
Experiments
interactions
integrity
molecular orbitals
stabilization
inversions
activation energy
orbitals
rings

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Ab initio MO study on [3 + 2] annulation using β-phenylthio-acryloylsilanes with alkyl methyl ketone enolates and its through-space/bond interaction analysis. / Orimoto, Yuuichi; Naka, Kazunari; Takeda, Kei; Aoki, Yuriko.

In: Organic and Biomolecular Chemistry, Vol. 3, No. 12, 21.06.2005, p. 2244-2249.

Research output: Contribution to journalArticle

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