Journal
ACS CATALYSIS
Volume 7, Issue 8, Pages 5151-5162Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b01296
Keywords
nucleophilic catalyst; Lewis base catalysis; asymmetric catalysis; iridium; chiral-at-metal; acyl transfer
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Funding
- Deutsche Forschungsgemeinschaft [ME 1805/11-1]
- Russian Science Foundation [17-13-01526]
- Russian Science Foundation [17-13-01526] Funding Source: Russian Science Foundation
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Herein, we report about the design, synthesis, and application of a nucleophilic octahedral chiral-only-at metal iridium(III) complex. We demonstrate that the enantiopure form of this complex serves as an efficient catalyst for the asymmetric Steglich rearrangement of O-acylated azlactones (up to 96% ee and 99% yield) and the related asymmetric Black rearrangement of O-acylated benzofuranones (up to 94% ee and 99% yield). We provide insight into the mechanisms of these two acyl migration reactions and the catalyst's manner of chiral recognition with crystal structures of the active catalyst and a catalysis intermediate analog, as well as with quantum chemical calculations based on them. Furthermore, we demonstrate that the presented catalyst also efficiently catalyzes the asymmetric reaction between aryl alkyl ketenes and 2-cyanopyrrole to give the corresponding alpha-chiral N-acyl pyrroles (up to 95% ee and 99% yield).
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