Towards Data‐Driven Design of Asymmetric Hydrogenation of Olefins: Database and Hierarchical Learning

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(42), P. 22804 - 22811

Published: Aug. 9, 2021

Abstract Asymmetric hydrogenation of olefins is one the most powerful asymmetric transformations in molecular synthesis. Although several privileged catalyst scaffolds are available, development for still a time‐ and resource‐consuming process due to lack predictive design strategy. Targeting data‐driven catalysis, we herein report standardized database that contains detailed information over 12000 literature hydrogenations olefins. This provides valuable platform machine learning applications catalysis. Based on this database, developed hierarchical approach achieve leaning model using only dozens enantioselectivity data with target olefin, which offers useful solution few‐shot problem will facilitate reaction optimization new olefin substrate catalysis screening.

Language: Английский

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Nickel/Copper‐Cocatalyzed Asymmetric Benzylation of Aldimine Esters for the Enantioselective Synthesis of α‐Quaternary Amino Acids

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(23)

Published: March 23, 2022

The first asymmetric Ni/Cu cocatalyzed benzylation of aldimine esters is reported. A series benzyl-substituted α-quaternary amino acids could be synthesized in high yield and with levels enantioselectivity (up to 90 % 99 ee). experimental theoretical calculation results suggested that the strong electrophilicity η3 -benzylnickel intermediate crucial for reactivity, enabling reaction under base-free conditions. Furthermore, this method has been applied synthesis cell adhesion inhibitor BIRT-377 analogues, key NK1 receptor antagonist PD154075 CCK-B CI-988.

Language: Английский

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Proton‐Promoted Nickel‐Catalyzed Asymmetric Hydrogenation of Aliphatic Ketoacids

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(15)

Published: Jan. 31, 2022

A robust and highly active homogeneous chiral nickel-phosphine complex for the asymmetric hydrogenation of aliphatic γ- δ-ketoacids has been discovered. The could proceed smoothly in presence 0.0133 mol% catalyst loading (S/C=7500). coordination chemistry catalytic behavior Ni(OTf)2 with (S,S)-Ph-BPE were explored by 1 H NMR HRMS. mechanistic studies revealed that a proton promoted activation substrate C=O bond controlled stereoselectivity through hydrogen bonds. series δ-alkyl substituted lactones obtained high yields excellent enantioselectivities (up to 98 % yield 99 ee). In addition, this system also demonstrated levulinic acid produced from biomass feedstock was converted into γ-valerolactone without loss ee value.

Language: Английский

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E-Selective Manganese-Catalyzed Semihydrogenation of Alkynes with H₂ Directly Employed or In Situ-Generated

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(4), P. 2253 - 2260

Published: Jan. 31, 2022

Selective semihydrogenation of alkynes with the Mn(I) alkyl catalyst fac-[Mn(dippe)(CO)3(CH2CH2CH3)] (dippe = 1,2-bis(di-iso-propylphosphino)ethane) as a precatalyst is described. The required hydrogen gas either directly employed or in situ-generated upon alcoholysis KBH4 methanol. A series aryl-aryl, aryl-alkyl, alkyl-alkyl, and terminal was readily hydrogenated to yield E-alkenes good excellent isolated yields. reaction proceeds at 60 °C for 60-90 loadings 0.5-2 mol %. implemented protocol tolerates variety electron-donating electron-withdrawing functional groups, including halides, phenols, nitriles, unprotected amines, heterocycles. can be upscaled gram scale. Mechanistic investigations, deuterium-labeling studies density theory (DFT) calculations, were undertaken provide reasonable mechanism, showing that initially formed Z-isomer undergoes fast isomerization afford thermodynamically more stable E-isomer.

Language: Английский

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Enzyme-like water preorganization in a synthetic molecular cleft for homogeneous water oxidation catalysis

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(10), P. 867 - 877

Published: Oct. 3, 2022

Language: Английский

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