Mechanistic study on the enantiodifferentiating anti-Markovnikov photoaddition of alcohols to 1,1-diphenyl-1-alkenes in near-critical and supercritical carbon dioxide

Yasuhiro Nishiyama, Masayuki Kaneda, Sadayuki Asaoka, Ryota Saito, Tadashi Mori, Takehiko Wada, Yoshihisa Inoue

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

Enantiodifferentiating anti-Markovnikov photoaddition of alcohol (methanol, ethanol, 2-propanol, and tert-butanol) to aromatic alkene (1,1-diphenylpropene and 1,1-diphenyl-1-butene), sensitized by optically active alkyl and saccharide naphthalene(di)carboxylates, was investigated in supercritical carbon dioxide at varying pressures to elucidate the effects of clustering on photosensitization and enantiodifferentiation behavior, in particular on the product's enantiomeric excess (ee). For all the alkene/alcohol/chiral sensitizer combinations examined, a sudden change in the product's ee was consistently observed near the critical density, which is attributable to the critical pressure dependence of clustering around the intervening exciplex intermediate.

Original languageEnglish
Pages (from-to)13432-13440
Number of pages9
JournalJournal of Physical Chemistry A
Volume111
Issue number51
DOIs
Publication statusPublished - 2007 Dec 27
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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