YfeX – A New Platform for Carbene Transferase Development with High Intrinsic Reactivity

Chemistry - A European Journal, Год журнала: 2022, Номер 28(65)

Опубликована: Авг. 11, 2022

Carbene transfer biocatalysis has evolved from basic science to an area with vast potential for the development of new industrial processes. In this study, we show that YfeX, naturally a peroxidase, great carbene transferases, due its high intrinsic reactivity, especially N-H insertion reaction aromatic and aliphatic primary secondary amines. YfeX shows stability against organic solvents (methanol DMSO), greatly improving turnover hydrophobic substrates. Interestingly, in styrene cyclopropanation, WT enantioselectivity, generating trans product 87 % selectivity (R,R) enantiomer. also catalyzes Si-H efficiently. Steric effects active site were further explored using R232A variant. Quantum Mechanics/Molecular Mechanics (QM/MM) calculations reveal details on mechanism insertion. potentially other peroxidases, are exciting targets improved transferases.

Язык: Английский

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A Carbene Relay Strategy for Cascade Insertion Reactions

Angewandte Chemie, Год журнала: 2023, Номер 135(45)

Опубликована: Сен. 19, 2023

Abstract Insertion reactions that involve stabilized electrophilic metallocarbenes are of great importance for installing α‐heteroatoms to carbonyl compounds. Nevertheless, the limited availability carbene precursors restricts introduction only a single heteroatom. In this report, we describe new approach based on an I (III) /S (VI) reagent promotes cascade insertion heteroatoms. This is achieved by sequentially generating two α‐heteroatom‐substituted metal carbenes in one reaction. We found mixed ylide reacts efficiently with transition catalyst and X−H bond (where X=O, N). transformation leads sequential formation sulfoxonium‐ X‐substituted Rh‐carbenes, enabling further another Y−H bond. Remarkably, wide range symmetrical unsymmetrical α,α‐ O , ‐, N ‐subsituted ketones can be prepared under mild ambient conditions. addition, successfully demonstrated other cascades, such as CN/CN double amidation, C−H/C−S insertion, C−S/Y−H Y=S, N, O, C). Notably, latter cascades enabled simultaneous installation three functional groups α‐carbon compounds step. These demonstrate versatility our approach, allowing synthesis esters multiple using common precursor.

Язык: Английский

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Self‐Supported Heterogeneous Dirhodium(II) Catalyst for Nitrene and Carbene Transfer Reactions

European Journal of Organic Chemistry, Год журнала: 2023, Номер 27(8)

Опубликована: Дек. 21, 2023

Abstract The bimetallic rhodium(II) paddlewheel (Rh 2 A 4 ) complex is one of the most reactive classes rhodium catalysts, well‐renowned for demanding carbene‐ and nitrene‐transfer reactions. In view its importance in modern synthetic chemistry, we herein report a facile approach preparing self‐supported reusable dirhodium(II) polymer‐based heterogeneous catalyst through reductive ligation protocol. displays good reactivity inter‐ intramolecular nitrene‐ carbene‐insertions various olefins, can also engage C−H insertion hydrocarbon derivatives, all under ambient conditions. reusability expected to empower use these precious metal catalysts at industrial scales.

Язык: Английский

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Enantioselective 1,3‐Dipolar Cycloaddition of Aryldiazoalkanes Catalyzed by Chiral Oxazaborolidinium Ions

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(8)

Опубликована: Июнь 30, 2023

Abstract Non‐stabilized aryldiazoalkanes were utilized for highly enantioselective catalytic 1,3‐dipolar cycloaddition reaction in the presence of chiral oxazaborolidinium ion (COBI) as a Lewis acid catalyst. Enantioenriched 2‐pyrazolines obtained excellent yields (up to >99%) with enantioselectivities >99%).

Язык: Английский

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Taming of Furfurylidenes by Chiral Bismuth‐Rhodium Paddlewheel Catalysts. Preparation and Functionalization of Optically Active 1,1‐Disubstituted (Trifluoromethyl)cyclopropanes

Angewandte Chemie, Год журнала: 2023, Номер 135(44)

Опубликована: Сен. 12, 2023

Abstract Although 2‐furyl‐carbenes (furfurylidenes) are prone to instantaneous electrocyclic ring opening, chiral [BiRh]‐paddlewheel complexes empowered by London dispersion allow (trifluoromethyl)furfurylidene metal be generated from a bench‐stable triftosylhydrazone precursor. These reactive intermediates engage in asymmetric [2+1] cycloadditions and hence open entry into valuable trifluoromethylated cyclopropane or ‐cyclopropene derivatives optically active form, which important building blocks for medicinal chemistry but difficult make otherwise.

Язык: Английский

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