Enantioselective synthesis of amino acids from ammonia

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(6), P. 571 - 577

Published: May 16, 2022

Language: Английский

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Enantioselective Formal Vinylogous N–H Insertion of Secondary Aliphatic Amines Catalyzed by a High-Spin Cobalt(II) Complex

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(25), P. 9648 - 9656

Published: June 21, 2021

Vinylcarbene insertion into the nitrogen–hydrogen (N–H) bond of amines allows direct access to α,β-unsaturated γ-amino acid derivatives, meeting a marked challenge in control regio- and enantioselectivities. Here, we report highly γ-selective enantioselective N–H bonds aliphatic or aromatic secondary with vinyl substituted α-diazo pyrazoleamides using high-spin chiral N,N′-dioxide/cobalt(II) complex catalyst. The method affords wide variety valuable optically active Z- E-type amides. Calculation reveals spin state change from quartet cobalt(II) doublet Co(II)-carbene species for facile Z-selective nucleophilic addition.

Language: Английский

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Dual Catalysis in Organic Synthesis: Current Challenges and New Trends

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 26(1)

Published: Dec. 9, 2022

Abstract Dual catalysis is one of the most powerful strategies for development chemical reactions in organic synthesis. This strategy can be divided into cooperative catalysis, relay and sequential according to actual mode operation communication between catalysts. In recent years, such has been applied a large number studies since it advantages of: 1) increasing reactivity enabling challenging transformations; 2) offering way controlling stereoselectivity asymmetric reactions, which traditional catalytic systems; 3) catalyze stereodivergent synthesis molecules bearing or more stereocenters from same starting materials. Perspective, intends introduce reader EurJOC special collection on Catalysis , aims summarize different categories dual demonstrate their benefits constructing new bonds selective manner. Finally, current challenges trends will also presented.

Language: Английский

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Enantioselective Synthesis of α-Trifluoromethyl Amines via Biocatalytic N–H Bond Insertion with Acceptor-Acceptor Carbene Donors

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(6), P. 2590 - 2602

Published: Feb. 2, 2022

The biocatalytic toolbox has recently been expanded to include enzyme-catalyzed carbene transfer reactions not occurring in Nature. Herein, we report the development of a strategy for synthesis enantioenriched α-trifluoromethyl amines through an asymmetric N-H insertion reaction catalyzed by engineered variants cytochrome c552 from Hydrogenobacter thermophilus. Using combination protein and substrate engineering, this metalloprotein scaffold was redesigned enable chiral amino esters with up >99% yield 95:5 er using benzyl 2-diazotrifluoropropanoate as donor. When diazo reagent varied, enantioselectivity enzyme could be inverted produce opposite enantiomers these products 99.5:0.5 er. This methodology is applicable broad range aryl amine substrates, it can leveraged obtain chemoenzymatic access β-trifluoromethyl-β-amino alcohols halides. Computational analyses provide insights into interplay protein- reagent-mediated control on reaction. work introduces first example carbenoid acceptor-acceptor donor, offers solution enantioselective α-trifluoromethylated valuable synthons medicinal chemistry bioactive molecules.

Language: Английский

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Combining nickel and squaramide catalysis for the stereodivergent α-propargylation of oxindoles

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(4), P. 322 - 331

Published: March 28, 2022

Language: Английский

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