Water-mediated deracemization of a bisporphyrin helicate assisted by diastereoselective encapsulation of chiral guests

Ousaka, Naoki; Yamamoto, Shinya; Iida, Hiroki; Iwata, Takuya; Ito, Shingo; Hijikata, Yuh; Irle, Stephan; Yashima, Eiji

doi:10.1038/s41467-019-09443-z

Water-mediated deracemization of a bisporphyrin helicate assisted by diastereoselective encapsulation of chiral guests

Journal Article · Fri Mar 29 00:00:00 EDT 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-019-09443-z· OSTI ID:1659567

Ousaka, Naoki ^[1]; Yamamoto, Shinya ^[1]; ^[1]; Iwata, Takuya ^[1]; Ito, Shingo ^[2]; ^[3]; ^[3]; ^[1]

Nagoya Univ. (Japan). Dept. of Molecular Design and Engineering
Nagoya Univ. (Japan). Dept. of Chemistry
Nagoya Univ. (Japan). Dept. of Chemistry and Inst. of Transformative Bio-Molecules (WPI-ITbM)

Deracemization is a powerful method by which a racemic mixture can be transformed into an excess of one enantiomer with the aid of chiral auxiliaries, but has been applied only to small chiral molecular systems. Here we report a deracemization of a racemic double-stranded spiroborate helicate containing a bisporphyrin unit upon encapsulation of chiral aromatic guests between the bisporphyrin. The chiral guest-included helicate is kinetically stable, existing as a mixture of right- and left-handed double helices, which eventually undergo an inversion of the helicity triggered by water resulting from the water-mediated reversible diastereoselective B-O bond cleavage/reformation of the spiroborate groups, thus producing an optically-active helicate with a high enantioselectivity. Quantum chemical calculations suggest that the stereospecific CH-π interactions between the porphyrin hydrogen atoms of the helicate and an aromatic pendant group of the chiral guest play a key role in the enhancement of the helical handedness of the helicate.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE; Japan Society for the Promotion of Science (JSPS)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1659567

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 10; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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