Palladium-Catalyzed Transformations of Alkyl C–H Bonds

Chemical Reviews, Год журнала: 2016, Номер 117(13), С. 8754 - 8786

Опубликована: Дек. 2, 2016

This Review summarizes the advancements in Pd-catalyzed C(sp3)-H activation via various redox manifolds, including Pd(0)/Pd(II), Pd(II)/Pd(IV), and Pd(II)/Pd(0). While few examples have been reported of alkane C-H bonds, many activation/C-C C-heteroatom bond forming reactions developed by use directing group strategies to control regioselectivity build structural patterns for synthetic chemistry. A number mono- bidentate ligands also proven be effective accelerating directed weakly coordinating auxiliaries, which provides great opportunities reactivity selectivity (including enantioselectivity) functionalization reactions.

Язык: Английский

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Год журнала: 2020, Номер 120(3), С. 1788 - 1887

Опубликована: Янв. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Язык: Английский

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New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Год журнала: 2020, Номер 120(5), С. 2613 - 2692

Опубликована: Фев. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Язык: Английский

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Organocatalysis in Inert C–H Bond Functionalization

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 9433 - 9520

Опубликована: Фев. 13, 2017

As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis C–H bond functionalization is well foreseeable, joint force along this line has been demonstrated to be a powerful approach making inert more viable, predictable, selective. In review, we provide comprehensive summary over past decades. The review arranged by types bonds including alkane C–H, arene vinyl as those activated benzylic allylic alpha heteroatom such nitrogen oxygen. each section, discussion classified explicit organocatalytic mode involved.

Язык: Английский

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Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Angewandte Chemie International Edition, Год журнала: 2017, Номер 57(1), С. 62 - 101

Опубликована: Дек. 5, 2017

Abstract The functionalization of C(sp 3 )−H bonds streamlines chemical synthesis by allowing the use simple molecules and providing novel synthetic disconnections. Intensive recent efforts in development new reactions based on C−H have led to its wider adoption across a range research areas. This Review discusses strengths weaknesses three main approaches: transition‐metal‐catalyzed activation, 1, n ‐hydrogen atom transfer, carbene/nitrene for directed unactivated bonds. For each strategy, scope, reactivity different bonds, position reacting relative directing group, stereochemical outcomes are illustrated with examples literature. aim this is provide guidance inspire future area.

Язык: Английский

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Transient Directing Groups for Transformative C–H Activation by Synergistic Metal Catalysis

Chem, Год журнала: 2017, Номер 4(2), С. 199 - 222

Опубликована: Дек. 21, 2017

Язык: Английский

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Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Год журнала: 2021, Номер 121(24), С. 14957 - 15074

Опубликована: Окт. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Язык: Английский

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HFIP in Organic Synthesis

Chemical Reviews, Год журнала: 2022, Номер 122(15), С. 12544 - 12747

Опубликована: Июль 17, 2022

1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability stabilize ionic species, transfer protons, and engage range of other intermolecular interactions. The use this exponentially increased the past decade become choice some areas, such as C–H functionalization chemistry. In review, following brief history HFIP an overview physical properties, literature examples reactions using or additive are presented, emphasizing effect each reaction.

Язык: Английский

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Advancing the Logic of Chemical Synthesis: C−H Activation as Strategic and Tactical Disconnections for C−C Bond Construction

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(29), С. 15767 - 15790

Опубликована: Окт. 19, 2020

The design of synthetic routes by retrosynthetic logic is decisively influenced the transformations available. Transition-metal-catalyzed C-H activation has emerged as a powerful strategy for C-C bond formation, with myriad methods developed diverse substrates and coupling partners. However, its uptake in total synthesis been tepid, partially due to their apparent intractability, well lack comprehensive guidelines implementation. This Review addresses these issues offers guide identify opportunities generate bonds processes. By comparing syntheses accomplished using traditional approaches recent methods, this demonstrates how enabled construction led more efficient strategies, execution previously unattainable tactical maneuvers. Finally, shortcomings existing processes are highlighted; illustrates some highlighted can be further economized adopting next-generation ligand-enabled approaches.

Язык: Английский

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Palladium-Catalyzed C(sp3)–H Bond Functionalization of Aliphatic Amines

Chem, Год журнала: 2019, Номер 5(5), С. 1031 - 1058

Опубликована: Фев. 1, 2019

Язык: Английский

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