Nickel/Cobalt-Catalyzed C(sp³)–C(sp³) Cross-Coupling of Alkyl Halides with Alkyl Tosylates

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(10), P. 9285 - 9291

Published: Sept. 4, 2019

The C(sp3)–C(sp3) cross-coupling of alkyl halides with tosylates has been developed by employing a combination nickel and nucleophilic cobalt catalysts in the presence manganese reductant. This method provides straightforward route to diverse set not only secondary–primary but also primary–primary linkages under mild conditions without using alkyl-metallic reagents. Mechanistic studies suggest formation radicals from both tosylates. Additionally, could be applied short-step synthesis histone deacetylase inhibitor, Vorinostat.

Language: Английский

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Carbonyl umpolung as an organometallic reagent surrogate

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10733 - 10742

Published: Jan. 1, 2021

Carbonyls can serve as surrogates for organometallic reagents via hydrazones.

Language: Английский

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Catalytic Generation of Carbanions through Carbonyl Umpolung

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(40), P. 21624 - 21634

Published: May 15, 2021

Abstract Carbonyl Umpolung is a powerful strategy in organic chemistry to construct complex molecules. Over the last few years, versatile catalytic approaches for generation of acyl anion equivalents from carbonyl compounds have been developed, but methods obtain alkyl carbanions fashion are still at an early stage. This Minireview summarizes recent progress through Umpolung. Two different can be utilized enable compounds: Wolff–Kishner reaction and single‐electron reduction imines. We discuss scope, mechanistic insights, synthetic applications as well potential future developments.

Language: Английский

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Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(10)

Published: Nov. 15, 2021

The simple and efficient conversion of carbonyl compounds into functionalized alkanes via deoxygenation is highly enabling in chemical synthesis. This Review covers the recent methodology development carboxyl deoxygenative functionalizations, highlighting some representative significant contributions this field. These advances are categorized based on reactivity patterns oxygenated feedstock compounds, including aldehydes, ketones carboxylic acids. Four types reactive intermediates arising from aldehydes during deoxygenation, namely, bis-electrophiles, carbenoids, bis-nucleophiles alkyl radical equivalents, presented, while acids mainly behave as tris-electrophiles when deoxygenated. In each subcategory, selected examples organized according to type bond formation discussed a generalized mechanistic perspective.

Language: Английский

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An Old Dog with New Tricks: Enjoin Wolff–Kishner Reduction for Alcohol Deoxygenation and C–C Bond Formations

Synlett, Journal Year: 2019, Volume and Issue: 30(13), P. 1508 - 1524

Published: June 13, 2019

The Wolff–Kishner reduction, discovered in the early 1910s, is a fundamental and effective tool to convert carbonyls into methylenes via deoxygenation under strongly basic conditions. For over century, numerous valuable chemical products have been synthesized by this classical method. reaction proceeds reversible formation of hydrazone followed deprotonation with strong base give an N-anionic intermediate, which affords product upon denitrogenation protonation. By examining mechanistic pathway century old carbonyl deoxygenation, we envisioned subsequently developed two unprecedented new types transformations: a) alcohol b) C–C bond formations various electrophiles including Grignard-type reaction, conjugate addition, olefination, diverse cross-coupling reactions. 1 Introduction 2 Background 3 Alcohol Deoxygenation 3.1 Ir-Catalyzed 3.2 Ru-Catalyzed 3.3 Mn-Catalyzed 4 Grignard-Type Reactions 4.1 Addition Hydrazones Aldehydes Ketones 4.2 Hydrazone Imines 4.3 CO2 4.4 Fe-Catalyzed 5 Conjugate 5.1 5.2 6 Cross-Coupling 6.1 Ni-Catalyzed Negishi-type Coupling 6.2 Pd-Catalyzed Tsuji–Trost Alkylation Reaction 7 Other 7.1 Olefination 7.2 Heck-Type 7.3 Ullmann-Type 8 Conclusion Outlook

Language: Английский

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HOME-Chemistry: hydrazone as organo-metallic equivalent

Pure and Applied Chemistry, Journal Year: 2023, Volume and Issue: 95(5), P. 465 - 474

Published: Jan. 10, 2023

The modern synthetic chemistry heavily relies on the use of stoichiometric organometallic reagents to react with various electrophiles. dependence quantities metals and often organic halides as precursors, in turn both produces copious amounts metal halide wastes well leads concerns future sustainability. Inspired by classical Wolff-Kishner reduction, our lab has recently developed a general strategy

Language: Английский

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Iron Hydride Radical Reductive Alkylation of Unactivated Alkenes

Organic Letters, Journal Year: 2019, Volume and Issue: 22(2), P. 684 - 688

Published: Dec. 30, 2019

Iron-catalyzed hydrogen atom transfer-mediated intermolecular C-C coupling reactions between alkenes and tosylhydrazones, followed by in situ cleavage of the tosylhydrazine intermediates using Et3N, are described. The process involves a new strategic bond disconnection resulting reductive alkylation nonactivated alkenes. reaction is operationally simple, proceeds under mild conditions, has wide substrate scope.

Language: Английский

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Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 134(10)

Published: Nov. 15, 2021

Abstract The simple and efficient conversion of carbonyl compounds into functionalized alkanes via deoxygenation is highly enabling in chemical synthesis. This Review covers the recent methodology development carboxyl deoxygenative functionalizations, highlighting some representative significant contributions this field. These advances are categorized based on reactivity patterns oxygenated feedstock compounds, including aldehydes, ketones carboxylic acids. Four types reactive intermediates arising from aldehydes during deoxygenation, namely, bis‐electrophiles, carbenoids, bis‐nucleophiles alkyl radical equivalents, presented, while acids mainly behave as tris‐electrophiles when deoxygenated. In each subcategory, selected examples organized according to type bond formation discussed a generalized mechanistic perspective.

Language: Английский

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Functions of bioinspired pyrrole cobalt complexes–recently developed catalytic systems of vitamin B12 related complexes and porphycene complexes–

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 470, P. 214690 - 214690

Published: July 7, 2022

Language: Английский

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Umpolung cross-coupling of polyfluoroarenes with hydrazones via activation of C–F bonds

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(63), P. 9323 - 9326

Published: Jan. 1, 2019

An umpolung strategy for the cross-coupling of polyfluoroarenes with various substituted hydrazones to construct C(sp²)–C(sp³) bonds is developed.

Language: Английский

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