Supramolecular Photochirogenesis with a Higher-Order Complex: Highly Accelerated Exclusively Head-to-Head Photocyclodimerization of 2-Anthracenecarboxylic Acid via 2:2 Complexation with Prolinol

Yuko Kawanami, Shin Ya Katsumata, Masaki Nishijima, Gaku Fukuhara, Kaori Asano, Takeyuki Suzuki, Cheng Yang, Asao Nakamura, Tadashi Mori, Yoshihisa Inoue

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

An unprecedented 2:2 complex was shown to intervene in the enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid (A) mediated by a hydrogen-bonding template l-prolinol (P) to accelerate the formation of chiral anti-head-to-head and achiral syn-head-to-head cyclodimers in >99% combined yield with enhanced enantioselectivities of up to 72% ee for the former. The supramolecular complexation and photochirogenic behaviors, as well as the plausible structures, of intervening Am·Pn complexes (m, n = 1 or 2) were elucidated by combined theoretical and experimental spectroscopic, photophysical, and photochemical studies. Furthermore, the photochemical chiral amplification was achieved for the first time by utilizing the preferential 2:2 complexation of A with homochiral P to give normalized product enantioselectivities higher than those of the template used. The present strategy based on the higher-order hydrogen-bonding motif, which is potentially applicable to a variety of carboxylic acids and β-aminoalcohols, is not only conceptually new and expandable to other (photo)chirogenic and sensing systems but also may serve as a versatile tool for achieving photochemical asymmetric amplification and constructing chiral functional supramolecular architectures.

Original languageEnglish
Pages (from-to)12187-12201
Number of pages15
JournalJournal of the American Chemical Society
Volume138
Issue number37
DOIs
Publication statusPublished - 2016 Sep 21

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Enantioselectivity
Complexation
Amplification
Hydrogen bonds
Acids
Carboxylic Acids
Carboxylic acids
prolinol
anthracene-1-carboxylic acid

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Supramolecular Photochirogenesis with a Higher-Order Complex : Highly Accelerated Exclusively Head-to-Head Photocyclodimerization of 2-Anthracenecarboxylic Acid via 2:2 Complexation with Prolinol. / Kawanami, Yuko; Katsumata, Shin Ya; Nishijima, Masaki; Fukuhara, Gaku; Asano, Kaori; Suzuki, Takeyuki; Yang, Cheng; Nakamura, Asao; Mori, Tadashi; Inoue, Yoshihisa.

In: Journal of the American Chemical Society, Vol. 138, No. 37, 21.09.2016, p. 12187-12201.

Research output: Contribution to journalArticle

Kawanami, Yuko ; Katsumata, Shin Ya ; Nishijima, Masaki ; Fukuhara, Gaku ; Asano, Kaori ; Suzuki, Takeyuki ; Yang, Cheng ; Nakamura, Asao ; Mori, Tadashi ; Inoue, Yoshihisa. / Supramolecular Photochirogenesis with a Higher-Order Complex : Highly Accelerated Exclusively Head-to-Head Photocyclodimerization of 2-Anthracenecarboxylic Acid via 2:2 Complexation with Prolinol. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 37. pp. 12187-12201.
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