Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(6)

Опубликована: Дек. 12, 2022

Chiral α-substituted ethylphosphonate and ethylphosphine oxide compounds are widely used in drugs, pesticides, ligands. However, their catalytic asymmetric synthesis is still rare. Of the only hydrogenation methods available at present, all cases use rare metal catalysts. Herein, we report an efficient earth-abundant transition-metal nickel catalyzed affording corresponding chiral products with up to 99 % yield, 96 ee (enantiomeric excess) (99 ee, after recrystallization) 1000 S/C (substrate/catalyst); this also first study on of terminal olefins using a catalyst under hydrogen atmosphere. The mechanism was investigated via deuterium-labelling experiments calculations which indicate that two added atoms come from gas. Additionally, it believed reaction involves NiII rather than Ni0 cyclic process based weak attractive interactions between Ni olefin substrate.

Язык: Английский

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Coordination Versatility of NHC-metal Topologies in Asymmetric Catalysis: Synthetic Insights and Recent Trends

Coordination Chemistry Reviews, Год журнала: 2022, Номер 478, С. 214922 - 214922

Опубликована: Дек. 15, 2022

Язык: Английский

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P-Stereogenic Ir-MaxPHOX: A Step toward Privileged Catalysts for Asymmetric Hydrogenation of Nonchelating Olefins

ACS Catalysis, Год журнала: 2023, Номер 13(5), С. 3020 - 3035

Опубликована: Фев. 14, 2023

The Ir-MaxPHOX-type catalysts demonstrated high catalytic performance in the hydrogenation of a wide range nonchelating olefins with different geometries, substitution patterns, and degrees functionalization. These air-stable readily available have been successfully applied asymmetric di-, tri-, tetrasubstituted (ee′s up to 99%). combination theoretical calculations deuterium labeling experiments led uncovering factors responsible for enantioselectivity observed reaction, allowing rationalization most suitable substrates these Ir-catalysts.

Язык: Английский

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cis-Selective Hydrogenation of Aryl Germanes: A Direct Approach to Access Saturated Carbo- and Heterocyclic Germanes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 4109 - 4118

Опубликована: Фев. 13, 2023

A catalytic approach of synthesizing the cis-selective saturated carbo- and heterocyclic germanium compounds (3D framework) is reported via hydrogenation readily accessible aromatic germanes (2D framework). Among numerous catalysts tested, Nishimura's catalyst (Rh2O3/PtO2·H2O) exhibited best reactivity with an isolated yield up to 96%. broad range substrates including synthesis unprecedented was explored. This selective strategy could tolerate several functional groups such as −CF3, −OR, −F, −Bpin, −SiR3 groups. The synthesized products demonstrated applications in coupling reactions newly developed aza-Giese-type addition reaction (C–N bond formation) from cyclic germane product. These versatile motifs can have a substantial value organic medicinal chemistry they show orthogonal while competing other partners boranes or silanes, acquiring three-dimensional structure high stability robustness.

Язык: Английский

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Copper‐Catalyzed Chemoselective Asymmetric Hydrogenation of C=O Bonds of Exocyclic α,β‐Unsaturated Pentanones

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(35)

Опубликована: Июнь 12, 2023

A highly chemoselective earth-abundant transition metal copper catalyzed asymmetric hydrogenation of C=O bonds exocyclic α,β-unsaturated pentanones was realized using H2 . The desired products were obtained with up to 99 % yield and 96 ee (enantiomeric excess) (99 ee, after recrystallization). corresponding chiral allylic pentanol can be converted into several bioactive molecules. mechanism investigated via deuterium-labelling experiments control experiments, which indicate that the keto-enol isomerization rate substrate is faster than also show Cu-H complex only catalyze chemoselectively reduction carbonyl group. Computational results multiple attractive dispersion interactions (MADI effect) between catalyst bulky substituents play important roles stabilize states reduce generation by-products.

Язык: Английский

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