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![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Vibrational circular dichroism towards asymmetric catalysis: chiral induction in substrates coordinated with
Hisako Sato1, Kazuyoshi Takimoto1, Jun Yoshida2
1Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan. sato.hisako.my@ehime-u.ac.jp.
Abstract:
Cu(ii) complexes containing RR- or SS-2,2'-isopropylidene-bis(4-phenyl-2-oxazoline) (denoted as [Cu(RR- or SS-oxa)]2+) are known to catalyse many asymmetric organic reactions. Herein, the source of enantioselectivity was investigated by vibrational circular dichroism (VCD) spectroscopy. An achiral β-diketonato ligand (denoted as LH), such as 1-phenyl-1,3-butanedione and dibenzoylmethane, was added to form [Cu(RR- or SS-oxa)L]+. Clear VCD peaks were obtained from a CDCl3 solution of [Cu(RR- or SS-oxa)]2+ or [Cu(RR- or SS-oxa)L]+ at 1000-1800 cm-1. It is to be noted that when LH was coordinated, a new VCD peak appeared at ∼1380 cm-1, which was assigned to the C-O asymmetric stretching vibration of L-. Theoretical simulation helped rationalise the results in terms of the transformation of coordinated L- into a twisted chiral form. The extent of steric control within the coordination sphere was demonstrated, revealing the first step for enantioselectivity during catalysis.
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