Metallaphotoredox-enabled deoxygenative arylation of alcohols

Nature, Journal Year: 2021, Volume and Issue: 598(7881), P. 451 - 456

Published: Aug. 31, 2021

Language: Английский

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Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(9), P. 3536 - 3543

Published: Feb. 23, 2021

As alcohols are ubiquitous throughout chemical science, this functional group represents a highly attractive starting material for forging new C–C bonds. Here, we demonstrate that the combination of anodic preparation alkoxy triphenylphosphonium ion and nickel-catalyzed cathodic reductive cross-coupling provides an efficient method to construct C(sp2)–C(sp3) bonds, in which free aryl bromides—both readily available chemicals—can be directly used as coupling partners. This paired electrolysis reaction features broad substrate scope bearing wide gamut functionalities, was illustrated by late-stage arylation several structurally complex natural products pharmaceuticals.

Language: Английский

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Reductive Cross-Coupling of Unreactive Electrophiles

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(17), P. 2491 - 2509

Published: Aug. 11, 2022

ConspectusTransition-metal-catalyzed reductive coupling of electrophiles has emerged as a powerful tool for the construction molecules. While major achievements have been made in field cross-couplings between organic halides and pseudohalides, an increasing number reports demonstrates reactions involving more readily available, low-cost, stable, but unreactive electrophiles. This account summarizes recent results our laboratory focusing on this topic. These findings typically include deoxygenative C–C alcohols, alkylation alkenyl acetates, C–Si chlorosilanes, C–Ge chlorogermanes.The alcohols with is synthetically appealing, potential chemistry remains to be disclosed. Our initial study focused reaction allylic aryl bromides by combination nickel Lewis acid catalysis. method offers selectivity that opposite classic Tsuji–Trost reactions. Further investigation benzylic led foundation dynamic kinetic cross-coupling strategy applications nickel-catalyzed arylation cobalt-catalyzed enantiospecific alkenylation alcohols. The titanium catalysis was later established produce carbon radicals directly from unactivated tertiary via C–OH cleavage. development their fragments delivers new methods all-carbon quaternary centers. shown high functionalization leaving primary secondary intact. Alkenyl acetates are inexpensive, environmentally friendly considered most attractive reagents. benzyl ammoniums alkyl mild approaches conversion ketones into aliphatic alkenes.Extensive studies enabled us extend cross-electrophile silicon germanium chemistry. harness ready availability chlorosilanes chlorogermanes suffer challenge low reactivity toward transition metals. Under catalysis, broad range couple well vinyl- hydrochlorosilanes. use partners formation functionalized alkylsilanes. seems less substrate-dependent, various common aryl, alkenyl, In general, functionalities such Grignard-sensitive groups (e.g., acid, amide, alcohol, ketone, ester), acid-sensitive ketal THP protection), fluoride chloride, bromide, tosylate mesylate, silyl ether, amine tolerated. provide access organosilicon organogermanium compounds, some which challenging obtain otherwise.

Language: Английский

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Nontraditional Fragment Couplings of Alcohols and Carboxylic Acids: C(sp³)–C(sp³) Cross-Coupling via Radical Sorting

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(14), P. 6185 - 6192

Published: March 30, 2022

Alcohols and carboxylic acids are among the most commercially abundant, synthetically versatile, operationally convenient functional groups in organic chemistry. Under visible light photoredox catalysis, these native synthetic handles readily undergo radical activation, resulting open-shell intermediates can subsequently participate transition metal catalysis. In this report, we describe C(sp3)–C(sp3) cross-coupling of alcohols through dual combination N-heterocyclic carbene (NHC)-mediated deoxygenation hypervalent iodine-mediated decarboxylation. This mild practical Ni-catalyzed radical-coupling protocol was employed to prepare a wide array alkyl–alkyl cross-coupled products, including highly congested quaternary carbon centers from corresponding tertiary or acids. We demonstrate applications methodology alcohol C1-alkylation formal homologation, as well late-stage functionalization drugs, natural biomolecules.

Language: Английский

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Metal-catalysed C–Het (F, O, S, N) and C–C bond arylation

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(16), P. 8903 - 8953

Published: Jan. 1, 2021

The formation of C–aryl bonds has been the focus intensive research over last decades for construction complex molecules from simple, readily available feedstocks.

Language: Английский

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Photocatalytic Dehydroxymethylative Arylation by Synergistic Cerium and Nickel Catalysis

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(13), P. 4896 - 4902

Published: March 23, 2021

Under mild reaction conditions with inexpensive cerium and nickel catalysts, easily accessible free alcohols can now be utilized as operationally simple robust carbon pronucleophiles in selective C(sp3)–C(sp2) cross-couplings. Facilitated by automated high-throughput experimentation, sterically encumbered benzoate ligands have been identified for complexes, enabling the synergistic cooperation of catalysis emerging metallaphotoredox catalysis. A broad range aromatic halides facilely employed this transformation, representing a new paradigm bond construction between aryl extrusion formaldehyde. Moreover, mechanistic investigations conducted, leading to identification tribenzoate cerium(III) complex viable intermediate.

Language: Английский

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Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO₂ via Photoredox Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(19), P. 8551 - 8559

Published: April 4, 2022

A new strategy for the direct cleavage of C(sp3)-OH bond has been developed via activation free alcohols with neutral diphenyl boryl radical generated from sodium tetraphenylborate under mild visible light photoredox conditions. This verified by cross-electrophile coupling and carbon dioxide synthesis carboxylic acids. Direct transformation a range primary, secondary, tertiary benzyl to acids achieved. Control experiments computational studies indicate that undergoes homolysis bond, generating alkyl radicals. After reducing into anion conditions, following carboxylation CO2 affords product.

Language: Английский

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Reductive Deoxygenative Functionalization of Alcohols by First‐Row Transition Metal Catalysis

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(13), P. 1637 - 1652

Published: Jan. 23, 2023

Comprehensive Summary Alcohols are among the most accessible functionalities. Catalytic deoxygenative functionalization of alcohols is highly synthetically appealing. While significant progress has been made on reactions with nucleophiles, electrophilic coupling partners remain a real challenge. This manuscript highlights advance in this direction, which mainly achieved by first‐row transition metals. The low‐valent titanium catalyst shown unique reactivity to homolytically cleave C—OH bonds. formed carbon radicals could either undergo reduction give protonation products or couple fragments form C—C chemistry initially realized using stoichiometric amount reagents and later extended catalytic variants. Nickel features variety oxidation states ranging from Ni 0 IV , both two‐electron oxidative addition single‐electron process involved their activation an electrophile. These properties enable nickel catalyze reductive R–X electrophiles. reaction first reported allylic alcohols, then benzylic and, very recently non‐activated alcohols. Recent effort resulted many invaluable methodologies that improve efficiency for construction aliphatic use cobalt copper catalysts not only expands substrate scope these but also shows new selectivity issues.

Language: Английский

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Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Language: Английский

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Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

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