Nickel‐Catalyzed Four‐Component Carbonylation of Ethers and Olefins: Direct Access to γ‐Oxy Esters and Amides

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 13, 2022

Abstract Multi‐component carbonylation of olefins, a reaction that installs both carbon–carbon(heteroatom) bond and carbonyl group across the double bond, is an attractive strategy for alkene functionalization. Herein, we developed novel nickel‐catalyzed four‐component olefins with ethers under low CO gas pressure. Using alcohols amines as partner, diverse γ ‐oxy‐substituted esters amides were produced in good yields excellent functional tolerance. Notably, Naftidrofuryl, medicine treatment cerebrovascular disease (CVD), can be synthesized by this process straightforwardly.

Язык: Английский

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Catalytic Multicomponent Synthesis ofC‐Acyl Glycosides by Consecutive Cross‐Electrophile Couplings

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 27, 2022

C-Acyl glycosides are versatile intermediates to natural products and medicinally relevant entities. Conventional cross-coupling strategies secure these molecules often relied on two-component manifolds in which a glycosyl precursor is coupled with an acyl donor (pre-synthesized or generated situ) under transition metal dual catalysis forge C-C bond. Here, we disclose three-component Ni-catalyzed reductive regime that facilitates the chemoselective union of halides, organoiodides commercially available isobutyl chloroformate as CO surrogate. The method tolerates multiple functionalities resulting obtained high diastereoselectivities. Theoretical calculations provide mechanistic rationale for unexpectedly chemoselectivity sequential cross-electrophile couplings. This approach enables expeditious assembly difficult-to-synthesize C-acyl glycosides, well late-stage keto-glycosylation oligopeptides.

Язык: Английский

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Nickel-Catalyzed Enantioselective Coupling of Acid Chlorides with α-Bromobenzoates: An Asymmetric Acyloin Synthesis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(50), С. 23019 - 23029

Опубликована: Дек. 8, 2022

The reaction of common acyl-metal species (acyl anion) with aldehydes to furnish acyloins has received much less attention and specifically was restricted using preformed stoichiometric reagents. Moreover, the (catalytic) enantioselective variants remain unexplored, asymmetric synthesis chiral met significant challenges in organic synthesis. Here, we uncover highly coupling acid chlorides α-bromobenzoates by nickel catalysis for producing enantioenriched protected α-hydroxy ketones (acyloins, >60 examples) high enantioselectivities (up 99% ee). successful execution this protocol enables formation a key ketyl radical from α-bromoalkyl benzoate situ generated corresponding aldehyde acyl bromide, which finally is captured acyl-Ni catalytically formed chlorides, thus avoiding use synthetic utility chemistry demonstrated downstream elaboration toward diverse set synthetically valuable building blocks biologically active compounds.

Язык: Английский

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Nickel-Catalyzed Carbonylation of Cyclopropanol with Benzyl Bromide for Multisubstituted Cyclopentenone Synthesis

Organic Letters, Год журнала: 2022, Номер 24(14), С. 2699 - 2704

Опубликована: Апрель 7, 2022

Herein, we reported a Ni-catalyzed carbonylation of cyclopropanol with benzyl bromide to afford multisubstituted cyclopentenone under 1 atm CO. The reaction proceeds through cascade bromides, followed by generation nickel homoenolate from cyclopropanols via β-C elimination 1,4-diketones, which undergoes intramolecular Aldol condensation furnish highly substituted derivatives in moderate good yields. exhibits high functional group tolerance broad substrate scope.

Язык: Английский

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Transition Metal Catalyzed Enantioselective Migratory Functionalization Reactions of Alkenes through Chain‐Walking

Chinese Journal of Chemistry, Год журнала: 2022, Номер 40(13), С. 1608 - 1622

Опубликована: Апрель 3, 2022

Comprehensive Summary “Chain‐walking” reactions could realize to modify a molecule at the position far away from active site. It has been hot topic in research field of organic synthesis. As number achievements have made by researchers, products transition metal‐catalyzed chain‐walking be obtained with good enantioselectivity. This review summarized researches on asymmetric catalyzed metal past decade. These works are classified according species catalysts.

Язык: Английский

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