Chiral ionic liquid-mediated photochirogenesis. Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid

Gaku Fukuhara, Takahiro Okazaki, Marco Lessi, Masaki Nishijima, Cheng Yang, Tadashi Mori, Andrea Mele, Fabio Bellina, Cinzia Chiappe, Yoshihisa Inoue

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid (AC-H) and its lithium salt (AC-Li) in chiral ionic liquid (CIL), (R)-1-(2,3-dihydroxypropyl)-3-methylimidazolium acetate {[(R)-GLYMI][AcO]}, gave a mixture of two head-to-tail (HT) and two head-to-head (HH) cyclodimers in HT/HH ratios of 1.3-1.7 (for AC-H) and 2.2-4.3 (for AC-Li) with low enantiomeric excesses (ee) of 0-3% for chiral syn-HT and anti-HH dimers. In contrast, irradiation of AC-H in an aqueous solution, containing cucurbit[8]uril (CB[8]) as a host and [(R)-GLYMI][AcO] or [(R)-GLYMI][Tf 2N] as a modifier of CB portals, afforded the HH dimers in 91-99% selectivity, although the anti-HH dimer was totally racemic. Interestingly, irradiation of AC-H in a dichloromethane solution, containing [(R)-GLYMI][AcO] as a chiral template, led to the formation of the HH-dimers in 98% selectivity with chiral anti-HH dimer in -14% ee, presumably by the dual ligation of two ACs to a CIL through electrostatic and hydrogen-bonding interactions.

Original languageEnglish
Pages (from-to)7105-7112
Number of pages8
JournalOrganic and Biomolecular Chemistry
Volume9
Issue number20
DOIs
Publication statusPublished - 2011 Oct 21
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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