One-Pot Chlorination and Cross-Electrophile Coupling of Alcohols with Aryl Chlorides DOI
Benjamin N. Ahern, Daniel J. Weix

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Although alkyl alcohols and aryl chlorides are the two most abundant substrate pools for cross-electrophile coupling, methods to couple them remain limited. Herein we demonstrate a simple procedure in situ deoxychlorination of followed by XEC with chlorides. A broad scope can be achieved tuning rate reaction via halide exchange. Key success is identification 1-chloro-N,N,2-trimethyl-1-propenylamine as mild, noninterfering halogenation reagent.

Язык: Английский

Metallaphotoredox-enabled deoxygenative arylation of alcohols DOI
Zhe Dong, David W. C. MacMillan

Nature, Год журнала: 2021, Номер 598(7881), С. 451 - 456

Опубликована: Авг. 31, 2021

Язык: Английский

Процитировано

307

Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides DOI
Zijian Li, Wenxuan Sun,

Xianxu Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(9), С. 3536 - 3543

Опубликована: Фев. 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.

Язык: Английский

Процитировано

205

Reductive Cross-Coupling of Unreactive Electrophiles DOI

Xiaobo Pang,

Pei‐Feng Su,

Xing‐Zhong Shu

и другие.

Accounts of Chemical Research, Год журнала: 2022, Номер 55(17), С. 2491 - 2509

Опубликована: Авг. 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.

Язык: Английский

Процитировано

170

Nontraditional Fragment Couplings of Alcohols and Carboxylic Acids: C(sp3)–C(sp3) Cross-Coupling via Radical Sorting DOI
Holt A. Sakai, David W. C. MacMillan

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(14), С. 6185 - 6192

Опубликована: Март 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.

Язык: Английский

Процитировано

154

Metal-catalysed C–Het (F, O, S, N) and C–C bond arylation DOI
Binlin Zhao, Torben Rogge, Lutz Ackermann

и другие.

Chemical Society Reviews, Год журнала: 2021, Номер 50(16), С. 8903 - 8953

Опубликована: Янв. 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.

Язык: Английский

Процитировано

116

Photocatalytic Dehydroxymethylative Arylation by Synergistic Cerium and Nickel Catalysis DOI
Yue-Gang Chen,

Xin Wang,

Xu He

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(13), С. 4896 - 4902

Опубликована: Март 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.

Язык: Английский

Процитировано

110

Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO2 via Photoredox Catalysis DOI
Wen‐Duo Li, Yang Wu, Shijun Li

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(19), С. 8551 - 8559

Опубликована: Апрель 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.

Язык: Английский

Процитировано

73

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

Xiaobo Pang,

Xing‐Zhong Shu

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(13), С. 1637 - 1652

Опубликована: Янв. 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.

Язык: Английский

Процитировано

52

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

Adam Cook,

Stephen G. Newman

Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 6078 - 6144

Опубликована: Апрель 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

Язык: Английский

Процитировано

40

Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis DOI Creative Commons
Lauren E. Ehehalt, Omar M. Beleh, Isabella C. Priest

и другие.

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 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

Язык: Английский

Процитировано

25