Branch-Selective Addition of Unactivated Olefins into Imines and Aldehydes

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(49), С. 16976 - 16981

Опубликована: Ноя. 21, 2018

Radical hydrofunctionalization occurs with ease using metal-hydride hydrogen atom transfer (MHAT) catalysis to couple alkenes and competent radicalophilic electrophiles. Traditional two-electron electrophiles have remained unreactive. Herein we report the reductive coupling of electronically unbiased olefins imines aldehydes. Iron allows addition alkyl-substituted into through intermediacy free radicals, whereas a combination catalytic Co(Salt-Bu,t-Bu) chromium salts enables branch-selective aldehydes formation putative alkyl intermediate.

Язык: Английский

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Cobalt-Catalyzed Intermolecular Hydrofunctionalization of Alkenes: Evidence for a Bimetallic Pathway

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(18), С. 7250 - 7255

Опубликована: Апрель 23, 2019

A functional group tolerant cobalt-catalyzed method for the intermolecular hydrofunctionalization of alkenes with oxygen- and nitrogen-based nucleophiles is reported. This protocol features a strategic use hypervalent iodine(III) reagents that enables mechanistic shift from conventional cobalt–hydride catalysis. Key evidence was found supporting unique bimetallic-mediated rate-limiting step involving two distinct cobalt(III) species, which new carbon–heteroatom bond formed.

Язык: Английский

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Nickel‐Catalyzed Asymmetric Synthesis of α‐Arylbenzamides

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(3), С. 1605 - 1609

Опубликована: Окт. 5, 2020

A nickel-catalyzed asymmetric reductive hydroarylation of vinyl amides to produce enantioenriched α-arylbenzamides is reported. The use a chiral bisimidazoline (BIm) ligand, in combination with diethoxymethylsilane and aryl halides, enables the regioselective introduction groups internal position olefin, forging new stereogenic center α N atom. neutral reagents mild reaction conditions provides simple access pharmacologically relevant motifs present anticancer, SARS-CoV PLpro inhibitors, KCNQ channel openers.

Язык: Английский

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Catalytic Radical–Polar Crossover Reactions of Allylic Alcohols

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(49), С. 16982 - 16987

Опубликована: Ноя. 27, 2018

Radical–polar crossover hydrofunctionalizations of tertiary allylic alcohols are described. Depending on the structure catalyst, corresponding epoxides or semipinacol rearrangement products selectively obtained in good yields. Experimental evidence points to participation alkylcobalt complexes as electrophilic intermediates.

Язык: Английский

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Iron and cobalt catalysis: new perspectives in synthetic radical chemistry

Chemical Society Reviews, Год журнала: 2020, Номер 49(23), С. 8501 - 8542

Опубликована: Янв. 1, 2020

Iron and cobalt complexes are at the origin of high valuable synthetic pathways involving radical intemediates.

Язык: Английский

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