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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Organocatalytic Asymmetric Synthesis of Indole-Based Chiral Heterocycles: Strategies, Reactions, and Outreach

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 53(2), P. 425 - 446

Published: Dec. 10, 2019

Indole-based chiral heterocycles constitute a class of important heterocyclic compounds that are found in numerous pharmaceuticals, functional materials, and catalysts or ligands. Catalytic asymmetric synthesis, for which the 2001 Nobel Prize Chemistry was awarded, has been demonstrated to be most efficient method accessing compounds. Therefore, catalytic synthesis indole-based attracted great interest from scientific community. However, strategies toward this goal rather limited, challenges remain field, such as metal contamination products, limited number platform molecules with versatile reactivity, reactions offer high step economy, atom excellent enantiocontrol. novel urgently needed. To achieve goal, our group developed series unique strategies, designing developing their corresponding organocatalytic access heterocycles. In Account, we describe efforts address remaining research field. Namely, have designed vinylindoles, indolylmethanols, arylindoles indole derivatives construction scaffolds structural diversity complexity. Based on reactivities these molecules, accomplished cycloaddition, cyclization, addition dearomatization economy Using wide range heterocycles, including five-membered seven-membered axially tetrasubstituted synthesized efficiency enantioselectivity. addition, investigated properties some bioactivities activities, showed potent anticancer activities promising catalysis. These results help elucidate potential applications drug development catalysts. The undoubtedly become will continue hot topic field catalysis synthesis. Our efforts, summarized not only open window future innovative but also inspire chemists worldwide confront prompt further advances.

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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Peptide-Based Supramolecular Systems Chemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(22), P. 13869 - 13914

Published: Sept. 14, 2021

Peptide-based supramolecular systems chemistry seeks to mimic the ability of life forms use conserved sets building blocks and chemical reactions achieve a bewildering array functions. Building on design principles for short peptide-based nanomaterials with properties, such as self-assembly, recognition, catalysis, actuation, are increasingly available. is starting address far greater challenge systems-level access complex functions that emerge when multiple interactions coordinated integrated. We discuss key features relevant design, including regulating order disorder, development active adaptive by considering kinetic thermodynamic aspects combinatorial dynamic covalent noncovalent interactions. Finally, we how structural concepts, preorganization induced fit, critical develop materials tunable photonic, electronic, catalytic properties. highlight examples where combined, resulting in display properties cannot be achieved without this level integration.

Language: Английский

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Organocatalytic Atroposelective Synthesis of Indole Derivatives Bearing Axial Chirality: Strategies and Applications

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(18), P. 2562 - 2580

Published: Sept. 2, 2022

Catalytic atroposelective syntheses of axially chiral compounds have stimulated extensive interest in multiple communities, such as synthetic chemistry, biochemistry, and materials science, because the intriguing characteristics atropisomerism. In particular, atropisomeric indole derivatives, which contain a kind five-membered heterocyclic framework, are widely distributed number natural alkaloids, biologically relevant compounds, ligands, organocatalysts. Hence, catalytic synthesis derivatives bearing axial chirality is considerable importance has become an emerging focus research. However, there substantial challenges associated with including remote ortho-substituents around axis, lower barrier for rotation, weaker configurational stability than that six-membered biaryls. Therefore, development effective strategies toward urgent task.In order to tackle these accomplish task, our group devised unique strategy designing indole-derived platform molecules developing organocatalytic enantioselective transformations synthesize derivatives; asymmetric organocatalysis tremendous advantages was research area recognized by Nobel Prize Chemistry 2021. This Account summarizes endeavors chirality. brief, we developed series molecules, indolylmethanols, (hetero)aryl indoles, oxindole-based styrenes, N-aminoindoles, indole-based homophthalic anhydrides, introducing different functional groups onto ring achieve new reactivity modulate reactive site ring. As result, possess versatile capable undergoing variety preparing structurally diversified chirality.We used plenty chirality, alkene-indoles, N-pyrrolylindoles, isochromenone-indoles. addition, gave thorough detailed understanding designed reaction investigating pathway activation mode. More importantly, studied biological activity some products performed catalyst design on basis moieties, helpful disclosing more applications chirality.In future, will indubitably remain frontier topic catalysis chemistry despite challenging issues, instance, novel unconventional into powerful catalysts or discovery potent drug candidates. We hope efforts summarized this encourage chemists worldwide devise innovative solving issues field, thus promoting its higher level.

Language: Английский

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Prebiotic Peptides: Molecular Hubs in the Origin of Life

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(11), P. 4707 - 4765

Published: Feb. 26, 2020

The fundamental roles that peptides and proteins play in today's biology makes it almost indisputable were key players the origin of life. Insofar as is appropriate to extrapolate back from extant prebiotic world, one must acknowledge critical importance interconnected molecular networks, likely with components, would have played life's origin. In this review, we summarize chemical processes involving could contributed early evolution, an emphasis on interactions between other classes organic molecules. We first mechanisms by which amino acids similar building blocks been produced elaborated into proto-peptides. Next, non-covalent well nucleic acids, lipids, carbohydrates, metal ions, aromatic molecules are discussed relation possible such evolution structure function. Finally, describe research structural alternatives covalent adducts acids/peptides propose ample future breakthroughs origin-of-life chemistry will stem investigations systems synergistic different emerge.

Language: Английский

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Enantioselective remote C–H activation directed by a chiral cation

Science, Journal Year: 2020, Volume and Issue: 367(6483), P. 1246 - 1251

Published: March 12, 2020

Chiral cations have been used extensively as organocatalysts, but their application to rendering transition metal-catalyzed processes enantioselective remains rare. This is despite the success of analogous charge-inverted strategy in which cationic metal complexes are paired with chiral anions. We report here a render common bipyridine ligand anionic and pair its iridium cation derived from quinine. applied these ion-paired long-range asymmetric induction desymmetrization geminal diaryl motif, located on carbon or phosphorus center, by C-H borylation. In principle, numerous classes could likewise be amenable this approach.

Language: 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, Journal Year: 2019, Volume and Issue: 141(37), P. 14938 - 14945

Published: Aug. 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.

Language: Английский

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Advances in asymmetric organocatalysis over the last 10 years

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: July 29, 2020

Beyond esoteric interest, organocatalysis has now become one major pillar of asymmetric catalysis. Here, we discuss how new activation modes are conquering challenging stereoselective transformations and the recent integration with emerging photo- electrocatalysis, as well artificial intelligence. Organocatalysis a (asymmetric) authors trends in organocatalytic for other fields, such photoredox catalysis electrosynthesis.

Language: Английский

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Progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(23), P. 3967 - 3998

Published: Jan. 1, 2020

This review summarizes the progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives and their applications total synthesis natural products, gives some insights into challenging issues this research field.

Language: Английский

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