Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Qian, Pu-Fan; Zhou, Tao; Shi, Bing-Feng

doi:10.1039/d3cc03592a

Cited by 20 publications

(4 citation statements)

References 190 publications

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“…Thus, the axially chiral alkenearenes have been much less investigated until recent years. [86][87][88][89] As a class of intermediate similar to the prominent ortho-quinone methides, Vinylidene ortho-quinone methides (VQMs) feature axial chirality due to their orthogonal π-bonds forming an allene motif. The disturbed aromaticity of the VQM led to its high Scheme 19.…”

Section: Formation Of Arylalkene Atropisomersmentioning

confidence: 99%

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Ye,

Yu,

Deng

et al. 2024

Adv Synth Catal

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The Friedel‐Crafts reaction stands as a powerful synthetic tool for C‐H functionalization of aromatic feedstocks, which is conventionally realized through electrophilic alkylation and acylation. The burgeoning interests in axially chiral compounds across diverse fields have spurred extensive exploration of this classic transformation for catalytic atroposelective synthesis. Consequently, the past decade has witnessed the rapid expansion of various non‐canonical Friedel‐Crafts reactions, including electrophilic arylation, alkenylation, halogenation, sulfenylation, and amination of aryl C‐H bonds, thereby delving into new chemical spaces. A range of catalytic atroposelective synthetic methods have been devised for these significant arene C‐H functionalization. This review provides a comprehensive overview of the cutting‐edge catalytic synthesis of atropoisomers through non‐canonical Friedel‐Crafts reactions, categorized into three parts based on the type of bond formation on the aromatics: C(sp2)‐C(sp3) bond formations, C(sp2)‐C(sp2) bond formations and C(sp2)‐heteroatom bond formations. The richness of electrophiles and the modulation of atroposelectivity by diverse chiral organocatalysts, particularly chiral Brønsted acids, are elucidated. We anticipate that the repertoire of asymmetric Friedel‐Crafts reaction will continue to flourish and to be demonstrated in not only scientific researches but also industrial organic synthesis.

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Section: Formation Of Arylalkene Atropisomersmentioning

confidence: 99%

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Ye,

Yu,

Deng

et al. 2024

Adv Synth Catal

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“…Axially chiral alkenes was first mentioned and proposed by Kawabata in 1991 during the research on the memory of chirality 22 . It is only in recent years that studies for their catalytic synthesis were initiated 23 – 25 . Accordingly, several typical synthetic methods have been developed to date 26 – 33 .…”

Section: Introductionmentioning

confidence: 99%

Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks

Wang,

Gu,

Zou

et al. 2024

Nat Commun

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The past century has witnessed a large number of reports on the Z/E isomerization of alkenes. However, the vast majority of them are still limited to the isomerization of di- and tri-substituted alkenes. The stereospecific Z/E isomerization of tetrasubstituted alkenes remains to be an underdeveloped area, thus lacking in a stereodivergent synthesis of axially chiral alkenes. Herein we report the atroposelective synthesis of tetrasubstituted alkene analogues by asymmetric allylic substitution-isomerization, followed by their Z/E isomerization via triplet energy transfer photocatalysis. In this regard, the stereodivergent synthesis of axially chiral N-vinylquinolinones is achieved efficiently. Mechanistic studies indicate that the benzylic radical generation and distribution are two key factors for preserving the enantioselectivities of axially chiral compounds.

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“…Herein, we report the cobalt/organophotoredox dual-catalysis-enabled CMCA of 1,5,10-enediynes, which can be prepared from readily available 1,6-diynes, ketones, and 2-iodobenzylphosphonate (Scheme C). This reaction proceeds via the site-selective allylic C(sp 3 )–H bond activation without the aid of DGs, affording axially chiral aryl alkenes . A combined experimental and computational mechanistic investigation revealed that the C(sp 3 )–H bond activation at the zeta -position to the metal center of a metallole intermediate proceeds through a σ-complex assisted metathesis (σ-CAM) .…”

Section: Introductionmentioning

confidence: 99%

Cobalt/Organophotoredox Dual-Catalysis-Enabled Cyclization of 1,5,10-Enediynes Involving Metallole-Mediated Remote C(sp³)–H Bond Activation Leading to Axially Chiral Aryl Alkenes

Yamada,

Koga,

Yasui

et al. 2024

ACS Catal.

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Transition-metal-catalyzed C(sp 3 )−H functionalization has been much less investigated compared to C(sp 2 )−H functionalization because the site-selectivity control in C(sp 3 )−H bond activation is much more challenging than that in C(sp 2 )−H bond activation. Site-selective C(sp 3 )−H functionalization without the assistance of directing groups is highly desirable, because the installation and removal of directing groups are not required. Hence, cycloaddition through a site-selective C−H bond activation triggered by the formation of metallacycles, such as metalloles, is a highly atom-and step-economical method for synthesizing complex carbo-and heterocycles from simple unsaturated substrates. Herein, we report the cobalt/photoredox dual-catalysisenabled cyclization of 1,5,10-enediynes via remote C(sp 3 )−H bond activation triggered by metallole formation, affording axially chiral aryl alkenes. Several control experiments and theoretical calculations suggest that the C(sp 3 )−H bond cleavage proceeds through σ-complex-assisted metathesis (σ-CAM) in the metallole intermediate.

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Abstract: Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Cited by 20 publications

References 190 publications

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks

Cobalt/Organophotoredox Dual-Catalysis-Enabled Cyclization of 1,5,10-Enediynes Involving Metallole-Mediated Remote C(sp³)–H Bond Activation Leading to Axially Chiral Aryl Alkenes

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Abstract: Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Cited by 20 publications

References 190 publications

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Catalytic Synthesis of Atropoisomers via Non‐Canonical Friedel‐Crafts Reactions

Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks

Cobalt/Organophotoredox Dual-Catalysis-Enabled Cyclization of 1,5,10-Enediynes Involving Metallole-Mediated Remote C(sp3)–H Bond Activation Leading to Axially Chiral Aryl Alkenes

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Cobalt/Organophotoredox Dual-Catalysis-Enabled Cyclization of 1,5,10-Enediynes Involving Metallole-Mediated Remote C(sp³)–H Bond Activation Leading to Axially Chiral Aryl Alkenes