Transition Metal‐Catalyzed Enantioselective C−H Functionalization via Chiral Transient Directing Group Strategies

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(45), С. 19773 - 19786

Опубликована: Июль 20, 2020

Abstract Transition metal‐catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline synthesis complex chiral molecules. Despite significant progress, traditional directing group‐enabled strategies require additional steps for installation and removal groups from target molecule. The recently developed asymmetric using transient ( c TDGs) offers a promising alternative that can circumvent this obstacle therefore simplify process. In Minireview, we briefly discuss advent recent advances emerging concept, with emphasis on discussing creation various stereogenic centers developments TDGs. Applications natural product ligand derivatizations are also discussed. We hope Minireview will highlight great potential strategy help inspire further endeavors.

Язык: Английский

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Catalytic Enantioselective Functionalizations of C–H Bonds by Chiral Iridium Complexes

Chemical Reviews, Год журнала: 2020, Номер 120(18), С. 10516 - 10543

Опубликована: Сен. 8, 2020

The development of catalytic enantioselective transformations, enabling the construction complex molecular scaffolds from simple precursors, has been a long-standing challenge in organic synthesis. Recent achievements transition-metal catalyzed functionalizations carbon–hydrogen (C–H) bonds represent promising pathway toward this goal. Over last two decades, iridium catalysis evolved as valuable tool stereocontrolled synthesis chiral molecules via C–H activation. iridium-based systems with various ligand classes, well studies their reaction mechanisms, resulted dynamic progress area. This review aims to present comprehensive picture by complexes emphasis on mechanisms activation step.

Язык: Английский

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Recent development in transition metal-catalysed C–H olefination

Chemical Science, Год журнала: 2021, Номер 12(8), С. 2735 - 2759

Опубликована: Янв. 1, 2021

Transition metal-catalysed functionalizations of inert C-H bonds to construct C-C represent an ideal route in the synthesis valuable organic molecules. Fine tuning directing groups, catalysts and ligands has played a crucial role selective bond (sp2 or sp3) activation. Recent developments these areas have assured high level regioselectivity olefination reactions. In this review, we summarized recent progress oxidative sp2 sp3 with special emphasis on distal, atroposelective, non-directed directed olefination. The scope, limitation, mechanism various transition reactions been described briefly.

Язык: Английский

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Transient imine directing groups for the C–H functionalisation of aldehydes, ketones and amines: an update 2018–2020

Organic & Biomolecular Chemistry, Год журнала: 2020, Номер 18(37), С. 7291 - 7315

Опубликована: Янв. 1, 2020

This review describes recent advances in C–H functionalisation using transient directing groups. Advances group design, new bond forming methodologies, regio- and stereoselective processes, mechanistic insights are discussed.

Язык: Английский

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Chiral Transient Directing Groups in Transition-Metal-Catalyzed Enantioselective C–H Bond Functionalization

ACS Catalysis, Год журнала: 2020, Номер 10(21), С. 12898 - 12919

Опубликована: Окт. 21, 2020

Transition-metal-catalyzed C–H bond functionalization has known a rapid evolution in the last years, offering modern strategies for reaching high molecular complexity step- and atom-economical way. Despite indisputable advances, selectivity issues still remain, given ubiquity of bonds on molecules; thus, several approaches have been developed to tackle this challenge. Among them, use transient directing group emerged as an effective tool, circumventing need extra synthetic steps install then cleave molecule. More recently, strategy successfully applied even more challenging transition-metal-catalyzed enantioselective functionalization. This review will highlight discuss main advances made chiral C(sp2)–H C(sp3)–H by transition-metal catalysis.

Язык: Английский

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Transient directing ligands for selective metal-catalysed C–H activation

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(9), С. 646 - 659

Опубликована: Июль 20, 2021

Язык: Английский

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Ruthenium(II)‐Catalyzed Asymmetric Inert C−H Bond Activation Assisted by a Chiral Transient Directing Group

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(9), С. 3475 - 3479

Опубликована: Дек. 23, 2019

Abstract A ruthenium(II)‐catalyzed asymmetric intramolecular hydroarylation assisted by a chiral transient directing group has been developed. series of 2,3‐dihydrobenzofurans bearing all‐carbon quaternary stereocenters have prepared in remarkably high yields (up to 98 %) and enantioselectivities >99 % ee ). By this methodology, novel total synthesis CB2 receptor agonist MDA7 successfully

Язык: Английский

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Palladium-catalyzed direct asymmetric C–H bond functionalization enabled by the directing group strategy

Chemical Science, Год журнала: 2020, Номер 11(47), С. 12616 - 12632

Опубликована: Янв. 1, 2020

In the past decade, selective C-C and C-heteroatom bond construction through palladium-catalyzed direct C-H functionalization has been extensively studied by employing a variety of directing groups. Within this category, asymmetric C(sp2)-H C(sp3)-H activation for highly enantiomerically enriched skeletons still progressed at slow pace. This minireview briefly introduces major advances in field via group strategy.

Язык: Английский

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Ligand‐Controlled Direct γ‐C−H Arylation of Aldehydes

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(8), С. 3078 - 3082

Опубликована: Ноя. 28, 2019

Abstract The first example of Pd II ‐catalyzed γ‐C(sp 3 )−H functionalization aliphatic and benzoheteroaryl aldehydes has been developed using a transient ligand an external ligand, concurrently. A wide array γ‐arylated were readily accessed without preinstalling internal directing groups. catalytic mechanism was studied by performing deuterium‐labelling experiments, which indicated that the bond cleavage is rate‐limiting step during reaction process. This could be performed on gram scale, also demonstrated its potential application in synthesis new mechanofluorochromic materials with blue‐shifted mechanochromic properties.

Язык: Английский

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C–H Bond Functionalization of Amines: A Graphical Overview of Diverse Methods

SynOpen, Год журнала: 2021, Номер 05(03), С. 173 - 228

Опубликована: Июль 1, 2021

This Graphical Review provides a concise overview of the manifold and mechanistically diverse methods that enable functionalization sp

Язык: Английский

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