Transition‐Metal‐Catalyzed Carboxylation Reactions with Carbon Dioxide

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(49), P. 15948 - 15982

Published: May 3, 2018

Driven by the inherent synthetic potential of CO2 as an abundant, inexpensive and renewable C1 chemical feedstock, recent years have witnessed renewed interest in devising catalytic fixations into organic matter. Although formation C-C bonds via fixation remained rather limited for a long period time, close look literature data indicates that carboxylation reactions entered new era exponential growth, evolving mature discipline allows streamlining synthesis carboxylic acids, building blocks utmost relevance industrial endeavors. These strategies generally proven broadly applicability convenient to perform. However, substantial challenges still need be addressed reinforcing cover metal-catalyzed area conceptual concise manner, delineating underlying principles are slowly emerging this vibrant expertise.

Language: Английский

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Intermolecular Metal-Catalyzed Reductive Coupling of Dienes, Allenes, and Enynes with Carbonyl Compounds and Imines

Chemical Reviews, Journal Year: 2018, Volume and Issue: 118(12), P. 6026 - 6052

Published: June 13, 2018

Metal-catalyzed reductive coupling has emerged as an alternative to the use of stoichiometric organometallic reagents in increasingly diverse range carbonyl and imine additions. In this review, diene, allene, enyne pronucleophiles intermolecular couplings are surveyed, along with related hydrogen autotransfer processes.

Language: Английский

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Recent Advances in Hydrometallation of Alkenes and Alkynes via the First Row Transition Metal Catalysis

Chinese Journal of Chemistry, Journal Year: 2018, Volume and Issue: 36(11), P. 1075 - 1109

Published: Aug. 20, 2018

Abstract Hydrometallation of alkenes and alkynes provides a straightforward route to access alkyl‐ or alkenyl‐metal reagents, which have wide range applications in organic transformations. In recent years, the first row transition metals (such as copper, nickel, cobalt, iron, etc .) emerged high activity selectivity this area with aid variety ligands. This review covers advances hydrometallation minimally functionalized unsaturated C—C bonds (including alkenes, alkynes, dienes, allenes, enynes, .), well transformations involving catalytic process via metal catalysis.

Language: Английский

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Visible‐Light‐Mediated Metal‐Free Difunctionalization of Alkenes with CO₂ and Silanes or C(sp³)−H Alkanes

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(52), P. 17220 - 17224

Published: Nov. 9, 2018

Catalytic alkene difunctionalization via Si-H and C-H activations represents an ideal atom- step-economic pathway for quick assembly of molecular complexity. We herein developed a visible-light-promoted metal-free alkenes using abundant CO2 readily available C(sp3 )-H bonds as feedstocks. Through the merger photoredox hydrogen-atom-transfer catalysis, variety value-added compounds, such β-silacarboxylic acids bearing γ-heteroatom (e.g., N, O, S) could be directly accessed from simple in redox-neutral fashion.

Language: Английский

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Visible-Light-Driven Reductive Carboarylation of Styrenes with CO₂ and Aryl Halides

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(18), P. 8122 - 8129

Published: April 20, 2020

The first example of visible-light-driven reductive carboarylation styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range iodides bromides were compatible this reaction. Moreover, pyridyl halides, alkyl even chlorides also viable method. These findings may stimulate the exploration novel Meerwein arylation-addition reactions user-friendly as radical sources photocatalytic utilization CO2.

Language: Английский

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Copper-Catalyzed Functionalization of 1,3-Dienes: Hydrofunctionalization, Borofunctionalization, and Difunctionalization

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(2), P. 1485 - 1499

Published: Dec. 18, 2019

The catalytic conversion of chemical feedstocks into products medicinal and agricultural value is a key theme across modern synthetic chemistry. As 1,3-dienes are readily available from industrial cracking processes, there great interest in the development sustainable methods for functionalization these simple molecules. Although initial developments this field have required precious-transition-metal catalysts, has been push toward use inexpensive, nontoxic, more abundant copper catalysts to promote functionalization. This Perspective covers many area copper-catalyzed 1,3-dienes, particular hydrofunctionalization, borofunctionalization, difunctionalization (e.g., diamination).

Language: Английский

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Photoredox Catalysis as a Strategy for CO₂ Incorporation: Direct Access to Carboxylic Acids from a Renewable Feedstock

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(17), P. 5492 - 5502

Published: July 23, 2018

Carbon dioxide is an attractive reagent for organic synthesis from the standpoint of global sustainability. Its widespread use, however, hampered by fact that it poorly reactive. New catalysts and technologies enable C-C bond constructions are thus high intrinsic value. This Minireview describes recent advances in area photoredox catalysis as enabling strategy promoting carboxylations.

Language: Английский

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Transition metal-catalyzed carboxylation of unsaturated substrates with CO2

Coordination Chemistry Reviews, Journal Year: 2018, Volume and Issue: 374, P. 439 - 463

Published: Aug. 4, 2018

Language: Английский

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CuH-Catalyzed Enantioselective Ketone Allylation with 1,3-Dienes: Scope, Mechanism, and Applications

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(12), P. 5062 - 5070

Published: Feb. 28, 2019

Chiral tertiary alcohols are important building blocks for the synthesis of pharmaceutical agents and biologically active natural products. The addition carbon nucleophiles to ketones is most common approach alcohol but traditionally relies on stoichiometric organometallic reagents that difficult prepare, sensitive, uneconomical. We describe a mild efficient method copper-catalyzed allylation using widely available 1,3-dienes as allylmetal surrogates. Homoallylic bearing wide range functional groups obtained in high yield with good regio-, diastereo-, enantioselectivity. Mechanistic investigations density theory (DFT) implicate situ formation rapidly equilibrating mixture isomeric copper(I) allyl complexes, from which Curtin–Hammett kinetics determine major isomer product. A stereochemical model provided explain diastereo- enantioselectivity this process. Finally, was applied preparation an drug, (R)-procyclidine, key intermediate several pharmaceuticals.

Language: Английский

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Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(2), P. 1060 - 1076

Published: Dec. 12, 2019

Catalytic enantioselective synthesis of small-molecule building blocks with allylic stereogenic centers is an important objective in organic synthesis, but preparing this motif wherein the adjacent olefin 1,2-disubstituted a single step tremendous challenge. Late-transition-metal-catalyzed intermolecular couplings nucleophiles and 1,3-dienes hydrofunctionalization reactions have quickly emerged as compelling approach to these related compounds. In Perspective, we illustrate how diene hydrofunctionalizations provided avenue complex, highly desirable chemical space that not readily accessed by other technologies. We also aim provide some insight into varying mechanistic pathways nuances myriad help inform future reaction catalyst design.

Language: Английский

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