Vibrational circular dichroism towards asymmetric catalysis: chiral induction in substrates coordinated with copper(ii) ions
文献信息
Hisako Sato, Kazuyoshi Takimoto, Jun Yoshida, Akihiko Yamagishi
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.
期刊推荐

Bioorganic & Medicinal Chemistry Letters

Journal of the Indian Institute of Science

Critical Reviews in Solid State and Materials Sciences

Electroanalysis

Main Group Chemistry

Journal of Asian Natural Products Research

Herald of the Russian Academy of Sciences

NDT & E International

Journal of Chemical Sciences

Polycyclic Aromatic Compounds
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.


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