Recent Advances in Catalytic Asymmetric Construction of Atropisomers

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4805 - 4902

Published: March 27, 2021

Atropisomerism is a stereochemical behavior portrayed by three-dimensional molecules that bear rotationally restricted σ bond. Akin to the well-represented point-chiral molecules, atropisomerically chiral compounds are finding increasing utilities in many disciplines where molecular asymmetry influential. This provides steady demand on atroposelective synthesis, numerous synthetic pursuits have been rewarded with conceptually novel and streamlined methods while expanding structural diversity of atropisomers. review summarizes key achievements stereoselective preparation biaryl, heterobiaryl, nonbiaryl atropisomers documented between 2015 2020. Emphasis placed strategies for each class, examples cited illustrate potential applications accessed atropochiral targets.

Language: Английский

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Recent advances in the synthesis of axially chiral biarylsviatransition metal-catalysed asymmetric C–H functionalization

Chemical Communications, Journal Year: 2019, Volume and Issue: 55(59), P. 8514 - 8523

Published: Jan. 1, 2019

Recent advances in the synthesis of axially chiral biarylsviatransition metal-catalysed asymmetric C–H functionalization are reported.

Language: Английский

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Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C–H Functionalization Reactions

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(35), P. 14025 - 14040

Published: Aug. 25, 2021

Transition-metal-catalyzed enantioselective C-H functionalization has become a powerful strategy for the formation of C-C or C-X bonds, enabling highly asymmetric synthesis wide range enantioenriched compounds. Atropisomers are widely found in natural products and pharmaceutically relevant molecules, have also applications as privileged frameworks chiral ligands catalysts. Thus, research into routes atropisomers garnered great interest recent years. In this regard, transition-metal-catalyzed emerged an atom-economic efficient toward their synthesis. Perspective, approaches by reactions summarized. The main focus here is on catalysis via Pd, Rh, Ir complexes, which been most frequently utilized catalysts among reported reactions. Finally, we discuss limitations available protocols give outlook possible future avenues research.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(45), P. 19773 - 19786

Published: July 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.

Language: Английский

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Transition Metal Catalyzed Enantioselective C(sp²)–H Bond Functionalization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 13748 - 13793

Published: Nov. 12, 2020

Direct catalytic transformation of C–H bonds to new functionalities has provided a powerful strategy synthesize complex molecular scaffolds in straightforward way. Unstinting efforts the synthetic community have helped overcome long-standing major challenge regioselectivity by introducing directing group concept. However, full potential cannot be realized unless activated are stereochemically controlled. The enantioselective bond functionalization could provide an imperative tool for sustainable way synthesizing chiral scaffolds. Despite intrinsic challenges achieving stereocontrol, developed different tools order achieve stereoselective functionalization. In this review, we discuss remarkable recent advances emerging area C(sp2)–H highlight and opportunities, emphasizing techniques so far.

Language: Английский

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Chiral Phosphoric Acid Catalyzed Atroposelective C−H Amination of Arenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(17), P. 6775 - 6779

Published: Feb. 4, 2020

N-arylcarbazole structures are important because of their prevalence in natural products and functional OLED materials. C-H amination arenes has been widely recognized as the most efficient approach to access these structures. Conventional strategies involving transition-metal catalysts suffer from confined substrate generality requirement exogenous oxidants. Organocatalytic enantioselective C-N chiral axis construction remains elusive. Presented here is first organocatalytic strategy for synthesis novel axially frameworks by assembly azonaphthalenes carbazoles. This reaction accommodates broad scope gives atropisomeric N-arylcarbazoles good yields with excellent enantiocontrol. not only offers an alternative metal-catalyzed cross-coupling, but also brings about opportunities exploitation structurally diverse N-aryl atropisomers

Language: Английский

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Atroposelective Synthesis of Axially Chiral Styrenes via an Asymmetric C–H Functionalization Strategy

Chem, Journal Year: 2020, Volume and Issue: 6(2), P. 497 - 511

Published: Jan. 9, 2020

Language: Английский

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Synthesis of Axially Chiral Styrenes through Pd‐Catalyzed Asymmetric C−H Olefination Enabled by an Amino Amide Transient Directing Group

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(16), P. 6576 - 6580

Published: Feb. 3, 2020

Abstract The atroposelective synthesis of axially chiral styrenes remains a formidable challenge due to their relatively lower rotational barriers compared the biaryl atropoisomers. Herein, we describe construction through Pd II ‐catalyzed C−H olefination, using bulky amino amide as transient auxiliary. Various were produced with good yields and high enantioselectivity (up 95 % yield 99 ee ). Carboxylic acid derivatives resulting showed superior enantiocontrol over counterparts in Co III enantioselective C(sp 3 )−H amidation thioamide. Mechanistic studies suggest that cleavage is enantioselectivity‐determining step.

Language: Английский

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Palladium-catalyzed enantioselective C–H functionalization via C–H palladation

Trends in Chemistry, Journal Year: 2022, Volume and Issue: 4(3), P. 220 - 235

Published: Jan. 20, 2022

Language: Английский

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Enantioselective Synthesis of N‐N Atropisomers by Palladium‐Catalyzed C−H Functionalization of Pyrroles

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 21, 2023

The catalytic asymmetric construction of N-N atropisomeric biaryls remains a formidable challenge. Studies them lag far behind studies the more classical carbon-carbon biaryl atropisomers, hampering meaningful development. Herein, first palladium-catalyzed enantioselective C-H activation pyrroles for synthesis atropisomers is presented. Structurally diverse indole-pyrrole possessing chiral axis were produced with good yields and high enantioselectivities by alkenylation, alkynylation, allylation, or arylation reactions. Furthermore, kinetic resolution trisubstituted heterobiaryls sterically demanding substituents was also achieved. Importantly, this versatile functionalization strategy enables iterative exquisite selectivity, expediting formation valuable, complex, atropisomers.

Language: Английский

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