Cobalt‐Catalyzed Enantioselective C−H Carbonylation towards Chiral Isoindolinones

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 11, 2024

Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed unprecedented catalyzed by inexpensive readily cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, parallel affording a broad range of chiral isoindolinones in good yields excellent enantioselectivities (up to 92 % yield 99 ee). synthetic potential this method was demonstrated asymmetric synthesis biological active compounds, such as (S)-PD172938 (S)-Pazinaclone. resulting also serve ligands cobalt-catalyzed annulation alkynes construct phosphorus stereocenter.

Language: Английский

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Nickel‐Catalyzed Asymmetric Hydroaryloxy‐ and Hydroalkoxycarbonylation of Cyclopropenes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: July 15, 2022

Abstract The asymmetric Reppe carbonylation reactions provide a straightforward access to α ‐chiral carbonyl compounds. reported paradigms predominantly adopted precious palladium as the catalyst. Here we report nickel‐catalyzed of cyclopropenes with phenyl formate and CO/ROH, respectively. This asymmetrical synthetic protocol features high atom economy, good functional group tolerance, which rapidly constructs polysubstituted cyclopropanecarboxylic derivatives excellent diastereo‐ enantioselectivity. utility is demonstrated by facile conversion chiral products into bioactive molecules such (−)‐Tranylcypromine (−)‐Lemborexant.

Language: Английский

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Progress on transition metal catalyzed asymmetric hydroesterification, hydrocarboxylation, and hydroamidation reactions of olefins

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6757 - 6773

Published: Jan. 1, 2022

Hydrocarboxylation, hydroesterification, and hydroamidation of olefins are fundamental transformations in organic synthesis. Asymmetric processes for these provide an effective straightforward approach to optically active carboxylic acids their derivatives, which highly useful compounds pharmaceuticals, materials, fine chemicals, etc. This review provides a brief summary the development asymmetric hydrocarboxylation, with CO its surrogates.

Language: Английский

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Recent Advances in Visible-Light-Mediated Amide Synthesis

Molecules, Journal Year: 2022, Volume and Issue: 27(2), P. 517 - 517

Published: Jan. 14, 2022

Visible-light photoredox catalysis has attracted tremendous interest within the synthetic community. As such, activation mode potentially provides a more sustainable and efficient platform for of organic molecules, enabling invention many controlled radical-involved reactions under mild conditions. In this context, amide synthesis via strategy received growing due to ubiquitous presence structural motif in numerous natural products, pharmaceuticals functionalized materials. Employing strategy, wide variety amides can be prepared effectively from halides, arenes even alkanes irradiation visible light. These methods provide robust alternative well-established strategies that involve condensation between carboxylic acid amine mediated by stoichiometric activating agent. review, representative progresses made on through light-mediated radical are summarized.

Language: Английский

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Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(8), P. 4925 - 4941

Published: Jan. 27, 2023

Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.

Language: Английский

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Photoinduced Five‐Component Radical Relay Aminocarbonylation of Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 24, 2023

Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double has remained substantial challenge, particularly more advanced multicomponent variants, despite their great potential value. Herein, we report visible-light-driven relay five-component aminocarbonylation reaction of unactivated alkenes using under metal-free conditions. This protocol provides access to valuable γ-trifluoromethyl α-ketoamides good yields high chemoselectivity. Crucial was identification distinct dual roles amine coupling partners, sequentially acting as electron donors formation photoactive donor-acceptor (EDA) complexes precursors then acceptor via nitrogen cations form carbamoyl radicals. Cross-coupling radicals acyl that are formed in an alkene-based process affords products.

Language: Английский

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Electro-reductive carboxylation of acyclic C(sp3)–C(sp3) bonds in aromatic hydrocarbons with CO2

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(10), P. 3366 - 3372

Published: Aug. 16, 2024

Language: Английский

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Asymmetric Double Hydroxycarbonylation of Alkynes to Chiral Succinic Acids Enabled by Palladium Relay Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(29)

Published: May 7, 2022

Abstract A Pd‐catalyzed asymmetric double hydroxycarbonylation of terminal alkynes was developed by using relay catalysis, providing a highly efficient route to chiral succinic acids (41 examples, 76–94 %, 94–99 % ee ). Key success the combinatorial use Pd precursor with two distinct phosphine ligands in one pot. The synthetic utilities this protocol were showcased facile synthesis key intermediates for pharmaceuticals.

Language: Английский

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Photoredox/Iron Dual-Catalyzed Insertion of Acyl Nitrenes into C–H Bonds

Organic Letters, Journal Year: 2022, Volume and Issue: 24(23), P. 4114 - 4118

Published: June 6, 2022

In this work, the use of N-acyloxybenzamides as efficient acyl nitrene precursors under photoredox/iron dual catalysis is reported. The resulting nitrenes could be captured by various types C-H bonds and S- or P-containing molecules. Mechanism investigations suggested that formation from N-acyloxybenzamide occurs a photoredox process, it believed in redox process oxidative N-H bond cleavage prior to reductive N-O N-acyloxybenzamide.

Language: Английский

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Nickel-Catalyzed Highly Selective Reductive Carbonylation Using Oxalyl Chloride as the Carbonyl Source

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(12), P. 8161 - 8168

Published: June 2, 2023

Nickel-catalyzed carbonylative cross-electrophile coupling which emerges as a powerful, efficient, and low-cost method for constructing challenging carbonyl derivatives has attracted increasing attention of organic chemists. To avoid the generation poisonous, volatile, inert nickel complex, it is critical to develop an cheap, easily available CO surrogate. Oxalyl chloride, cheap commercially chemical, one most versatile reagents used in chemical reactions. In this work, high chemoselectivity can be achieved with 1:1:1 ratio Ar–I alkyl-I oxalyl chloride. A wide range alkyl aryl ketones present important class molecules synthetic medicinal chemistry are accessed from halides, iodides, under mild conditions. Primary secondary iodides were suitable substrates. Various functional groups well tolerated, affording up 90% yields. This protocol was also derivatization natural products drug molecules. Mechanistic investigation indicates that reaction Zn chloride conditions could release slowly. knowledge should useful further development multicomponent cross-coupling

Language: Английский

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