Recent developments in nickel-catalyzed asymmetric cyclization and cycloaddition of carbonyl-alkynes, cyano-alkynes, and enynes

Yan, Jun; Shi, Min; Wei, Yin

doi:10.1039/d3cc00520h

Cited by 7 publications

(1 citation statement)

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“…This approach is advantageous for introducing stereocenters into the ring skeleton during the ring-closure process. [16][17] An outstanding study by Tong group detailed a palladium-catalyzed hydroacyloxylative 7-endo-trig cyclization of nitrogen-tethered 1,6-enynes through an unusual E-to-Z vinyl-Pd(II) isomerization (Scheme 1f). [18] To the best of our knowledge, this is the only example capable of enantioselectively accessing C(sp 3)-rich azepine derivatives through alkyne functionalization.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine^†

Long,

Lu,

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryThe azepine ring is a prominent structural scaffold in biologically significant molecules. In this study, we present a Ni(II)‐catalyzed asymmetric difunctionalization of alkynes, involving intermolecular regioselective arylation and intramolecular nitrile addition, enabling the synthesis of enantioenriched azepine derivatives. This reaction simultaneously establishes an all‐carbon quaternary stereocenter and introduces an unprotected imine functionality, showing great promise for subsequent transformations. The reaction exhibits good tolerance toward various functional groups, resulting in high yields and enantioselectivities. The synthetic utility of this methodology is further demonstrated through gram‐scale synthesis and product derivatization. This research offers an alternative approach to the synthesis of seven‐membered nitrogen heterocycles.This article is protected by copyright. All rights reserved.

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Section: Background and Originality Contentmentioning

confidence: 99%

Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine^†

Long,

Lu,

et al. 2024

Chin. J. Chem.

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Recent Advances in Copper‐Catalyzed Oxidative Cyclization Reactions

Zhang

2024

Asian J Org Chem

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In this review, we have presented an overview on the copper‐catalyzed oxidative cyclization reactions over the period from 2020 to the present. In general, both Cu(II) and Cu(I) can be used as starting catalysts, but the reaction mechanism was different. For example, from the perspective of reaction mechanism, as a starting catalyst, Cu(II) was often directly combined with oxidants to participate in the catalytic oxidation of intermediates or substrates. When Cu(I) served as the starting catalyst, it directly promoted the cleavage of N‐O bonds or coordinated with alkyne bonds, while oxidants were used for the subsequent oxidation of intermediates. The experimental results showed that most of the copper‐catalyzed oxidative cyclization strategies have achieved satisfactory results.

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Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐Selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones

Li,

Deng,

Long

et al. 2024

Angewandte Chemie

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Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn‐hydrometalative 4‐exo‐trig cyclization of alkynones to synthesize alkenyl cyclobutanols with a tetrasubstituted stereocenter. This strategy features a broad substrate scope, delivering a variety of trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields and high enantioselectivities (up to 84% yield and 98.5:1.5 er). The synthetic utility is demonstrated through stereospecific transformations into fused spirocycles. Experimental and computational mechanistic studies indicate that the reaction is initiated by an active Ni–H species, with carbonyl‐directed hydrometalation as the key for regioselective control. This catalytic method provides a general solution for regioselective hydrofunctionalization of alkynes and represents an efficient reaction pattern for assembling highly strained enantioenriched bioisosteres.

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Recent developments in nickel-catalyzed asymmetric cyclization and cycloaddition of carbonyl-alkynes, cyano-alkynes, and enynes

Abstract: Alkynes as unsaturated hydrocarbons have long been used for cyclization reactions. Various transition metal-catalyzed cyclizations of alkynes have been reported in the past decades. In this minireview, we mainly summarize...

Cited by 7 publications

References 122 publications

Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine^†

Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine^†

Recent Advances in Copper‐Catalyzed Oxidative Cyclization Reactions

Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐Selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones

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Recent developments in nickel-catalyzed asymmetric cyclization and cycloaddition of carbonyl-alkynes, cyano-alkynes, and enynes

Abstract: Alkynes as unsaturated hydrocarbons have long been used for cyclization reactions. Various transition metal-catalyzed cyclizations of alkynes have been reported in the past decades. In this minireview, we mainly summarize...

Cited by 7 publications

References 122 publications

Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine†

Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine†

Recent Advances in Copper‐Catalyzed Oxidative Cyclization Reactions

Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐Selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones

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Product

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Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine^†

Ni‐Catalyzed Enantioselective Difunctionalization of Alkynes to Azepine Derivatives Bearing a Quaternary Center and an Unprotected Imine^†