Recent Advances in Catalytic Asymmetric Construction of Atropisomers

Chemical Reviews, Год журнала: 2021, Номер 121(8), С. 4805 - 4902

Опубликована: Март 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.

Язык: Английский

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

Chemical Communications, Год журнала: 2019, Номер 55(59), С. 8514 - 8523

Опубликована: Янв. 1, 2019

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

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(35), С. 14025 - 14040

Опубликована: Авг. 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.

Язык: Английский

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Atroposelective transformation of axially chiral (hetero)biaryls. From desymmetrization to modern resolution strategies

Chemical Society Reviews, Год журнала: 2021, Номер 50(5), С. 2968 - 2983

Опубликована: Янв. 1, 2021

Atroposelective transformations of (hetero)biaryls are classified into desymmetrization, kinetic resolution, dynamic and asymmetric transformation depending on the nature behavior starting material.

Язык: Английский

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Catalytic Asymmetric Construction of Axially Chiral Indole‐Based Frameworks: An Emerging Area

Chemistry - A European Journal, Год журнала: 2020, Номер 26(68), С. 15779 - 15792

Опубликована: Май 4, 2020

Axially chiral indole-based frameworks have been recognized as a class of important five-membered heterobiaryls and developing catalytic asymmetric approaches for constructing these in an enantioselective manner is highly desirable. In recent years, synthetic chemists paid much attention to this research field, rapid developments occurred. At point, range axially scaffolds constructed via various reactions based on different strategies. Thus, the construction has become emerging area. This minireview summarizes advances field gives some insights into future developments, which will help thrive.

Язык: Английский

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Enantioselective Pallada‐Electrocatalyzed C−H Activation by Transient Directing Groups: Expedient Access to Helicenes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(32), С. 13451 - 13457

Опубликована: Апрель 3, 2020

Abstract Asymmetric pallada‐electrocatalyzed C−H olefinations were achieved through the synergistic cooperation with transient directing groups. The electrochemical, atroposelective activations realized high position‐, diastereo‐, and enantio‐control under mild reaction conditions to obtain highly enantiomerically‐enriched biaryls fluorinated N−C axially chiral scaffolds. Our strategy provided expedient access to, among others, novel BINOLs, dicarboxylic acids helicenes of value asymmetric catalysis. Mechanistic studies by experiments computation key insights into catalyst's mode action.

Язык: Английский

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A Bulky Chiral N-Heterocyclic Carbene Palladium Catalyst Enables Highly Enantioselective Suzuki–Miyaura Cross-Coupling Reactions for the Synthesis of Biaryl Atropisomers

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(37), С. 14938 - 14945

Опубликована: Авг. 28, 2019

Axially chiral biaryl scaffolds are essential structural units in chemistry. The asymmetric Pd-catalyzed Suzuki–Miyaura cross-coupling reaction has been widely recognized as one of the most practical methods for constructing atropisomers biaryls. However, longstanding challenges remain this field. For example, substrate scope is often narrow and specialized, functional groups heterocycles can lead to reduced reactivity selectivity, bulky ortho-substituents usually needed, reported generally inapplicable tetra-ortho-substituted We have developed an unprecedented highly enantioselective N-heterocyclic carbene (NHC)-Pd catalyzed synthesis atropisomeric These reactions enable efficient coupling aryl halides (Br, Cl) or triflates with various types boron compounds (B(OH)2, Bpin, Bneo, BF3K), tolerate a remarkably broad (>41 examples), employ low loading catalyst (0.2–2 mol %), proceed under mild conditions. protocol provided general access biaryls heterobiaryls excellent enantioselectivities (up 99% ee) no need using ortho-substituted substrates was effective tetra-ortho-substituent Moreover, method successfully applied diastereo- ternaphthalenes. Critical success development application extremely C2-symmetric NHC, (R,R,R,R)-DTB-SIPE, ligand palladium. To best our knowledge, first (>90% example NHC-metal-catalyzed C(sp2)–C(sp2) reaction.

Язык: Английский

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

ACS Catalysis, Год журнала: 2020, Номер 10(23), С. 13748 - 13793

Опубликована: Ноя. 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.

Язык: Английский

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

Chem, Год журнала: 2020, Номер 6(2), С. 497 - 511

Опубликована: Янв. 9, 2020

Язык: Английский

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A Strategy for Synthesizing Axially Chiral Naphthyl‐Indoles: Catalytic Asymmetric Addition Reactions of Racemic Substrates

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(42), С. 15104 - 15110

Опубликована: Авг. 23, 2019

Abstract A new strategy for enantioselective synthesis of axially chiral naphthyl‐indoles has been established through catalytic asymmetric addition reactions racemic with bulky electrophiles. Under phosphoric acid catalysis, azodicarboxylates and o ‐hydroxybenzyl alcohols served as but reactive electrophiles that were attacked by C2‐unsubstituted naphthyl‐indoles, which underwent a dynamic kinetic resolution to afford two series in good yields (up 98 %) high enantioselectivities 98:2 er).

Язык: Английский

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