Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis DOI Creative Commons
Xiaomin Shu,

De Zhong,

Qian Huang

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 9, 2023

Abstract Site- and enantioselective cross-coupling of saturated N -heterocycles carboxylic acids—two the most abundant versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report general strategy for highly site- α-acylation with situ-activated acids. This modular approach exploits hydrogen-atom-transfer reactivity photocatalytically generated chlorine radicals combination asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds presence benzylic, allylic, acyclic α-amino, α-oxy methylene groups. The mild scalable protocol requires no organometallic reagents, displays excellent chemo-, enantioselectivity, is amenable late-stage diversification, including synthesis previously inaccessible Taxol derivatives. Mechanistic studies highlight exceptional versatility chiral catalyst orchestrating (i) catalytic elimination, (ii) alkyl radical capture, (iii) cross-coupling, (iv) induction.

Язык: Английский

Photocatalytic Late-Stage C–H Functionalization DOI
Peter Bellotti, Huan‐Ming Huang,

Teresa Faber

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Язык: Английский

Процитировано

319

A field guide to flow chemistry for synthetic organic chemists DOI Creative Commons
Luca Capaldo, Zhenghui Wen, Timothy Noël

и другие.

Chemical Science, Год журнала: 2023, Номер 14(16), С. 4230 - 4247

Опубликована: Янв. 1, 2023

This review explores the benefits of flow chemistry and dispels notion that it is a mysterious “black box”, demonstrating how can push boundaries organic synthesis through understanding its governing principles.

Язык: Английский

Процитировано

191

Radical C(sp3)–H functionalization and cross-coupling reactions DOI
Dung L. Golden, Sung‐Eun Suh, Shannon S. Stahl

и другие.

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(6), С. 405 - 427

Опубликована: Май 17, 2022

Язык: Английский

Процитировано

186

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis DOI Creative Commons
Rens Ham, C. Jasslie Nielsen,

Sonja Pullen

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(9), С. 5225 - 5261

Опубликована: Янв. 20, 2023

Because sunlight is the most abundant energy source on earth, it has huge potential for practical applications ranging from sustainable supply to light driven chemistry. From a chemical perspective, excited states generated by make thermodynamically uphill reactions possible, which forms basis storage into fuels. In addition, with light, open-shell species can be open up new reaction pathways in organic synthesis. Crucial are photosensitizers, absorb and transfer substrates various mechanisms, processes that highly depend distance between molecules involved. Supramolecular coordination cages well studied synthetically accessible vessels single cavities guest binding, ensuring close proximity of different components. Due high modularity their size, shape, nature metal centers ligands, ideal platforms exploit preorganization photocatalysis. Herein we focus application supramolecular photocatalysis artificial photosynthesis photo(redox) catalysis. Finally, brief overview immobilization strategies provides tools implementing devices. This review inspiration future design photocatalytic host-guest systems producing solar fuels complex molecules.

Язык: Английский

Процитировано

165

Photoelectrochemical asymmetric catalysis enables site- and enantioselective cyanation of benzylic C–H bonds DOI

Chen-Yan Cai,

Xiao‐Li Lai, Yu Wang

и другие.

Nature Catalysis, Год журнала: 2022, Номер 5(10), С. 943 - 951

Опубликована: Окт. 10, 2022

Язык: Английский

Процитировано

156

Electrochemical Late-Stage Functionalization DOI Creative Commons
Yulei Wang, Suman Dana, Hao Long

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335

Опубликована: Сен. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Язык: Английский

Процитировано

135

Photobiocatalytic Strategies for Organic Synthesis DOI
Megan A. Emmanuel, Sophie G. Bender,

Catherine Bilodeau

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(9), С. 5459 - 5520

Опубликована: Апрель 28, 2023

Biocatalysis has revolutionized chemical synthesis, providing sustainable methods for preparing various organic molecules. In enzyme-mediated most reactions involve molecules operating from their ground states. Over the past 25 years, there been an increased interest in enzymatic processes that utilize electronically excited states accessed through photoexcitation. These photobiocatalytic a diverse array of reaction mechanisms are complementary to one another. This comprehensive review will describe state-of-the-art strategies photobiocatalysis synthesis until December 2022. Apart reviewing relevant literature, central goal this is delineate mechanistic differences between general employed field. We organize based on relationship photochemical step and transformations. The include studies, substrate scopes, protein optimization strategies. By clearly defining mechanistically-distinct chemistry, we hope illuminate future synthetic opportunities area.

Язык: Английский

Процитировано

132

Iron-Catalyzed C(Sp3)–H Borylation, Thiolation, and Sulfinylation Enabled by Photoinduced Ligand-to-Metal Charge Transfer DOI
Jia‐Lin Tu,

Ao-Men Hu,

Lin Guo

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(13), С. 7600 - 7611

Опубликована: Март 23, 2023

Catalytic C(sp3)-H functionalization has provided enormous opportunities to construct organic molecules, facilitating the derivatization of complex pharmaceutical compounds. Within this framework, direct hydrogen atom transfer (HAT) photocatalysis becomes an appealing approach goal. However, viable substrates utilized in these protocols are limited, and site selectivity shows preference activated thermodynamically favored bonds. Herein, we describe development undirected iron-catalyzed borylation, thiolation, sulfinylation reactions enabled by photoinduced ligand-to-metal charge (LMCT) process. These exhibit remarkably broad substrate scope (>150 examples total), most importantly, all three show unconventional regioselectivity, with occurrence preferentially at distal methyl position. The procedures operationally simple readily scalable provide access high-value products from hydrocarbons one step. Mechanistic studies control experiments indicate that afforded is not only relevant HAT species but also largely affected use boron- sulfone-based radical acceptors.

Язык: Английский

Процитировано

116

Switchable Divergent Synthesis Using Photocatalysis DOI
Yota Sakakibara, Kei Murakami

ACS Catalysis, Год журнала: 2022, Номер 12(3), С. 1857 - 1878

Опубликована: Янв. 20, 2022

A highly selective and divergent synthesis enables access to various molecules has garnered broad interest from not only organic chemists but also medicinal biologists who work with chemical libraries. Since the 20th century, such transformations have been achieved using transition-metal-catalyzed reactions, in which choice of catalyst or ligand crucially affects selectivity. Over past several decades, photocatalysts attracted a considerable amount attention because they provide additional ways control reaction intermediates product selectivity via electron energy transfer. From this perspective, we highlight recent development switchable syntheses photocatalysts, are difficult achieve classical catalytic transformations.

Язык: Английский

Процитировано

113

Electronic control over site-selectivity in hydrogen atom transfer (HAT) based C(sp3)–H functionalization promoted by electrophilic reagents DOI
Marco Galeotti, Michela Salamone, Massimo Bietti

и другие.

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2171 - 2223

Опубликована: Янв. 1, 2022

Leveraging on electronic effects in both the substrate and HAT reagent, site-selectivity can be implemented C(sp 3 )–H bond functionalization.

Язык: Английский

Процитировано

99