Bimetallic Catalysis in Stereodivergent Synthesis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(45)

Published: Aug. 2, 2022

Abstract Bimetallic catalysis has emerged as an efficient strategy for the development of new chemical reactions. Importantly, this also provides a simple and powerful platform stereodivergent synthesis, whereby all possible stereoisomers products bearing two stereocenters can be easily prepared from same set starting materials. In Minireview, allylic substitution, propargylic hydrofunctionalization, annulation based on bimetallic been summarized. It is expected that more catalytic systems will developed applied synthesis valuable molecules.

Language: Английский

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Stereodivergent Synthesis of Enantioenriched γ‐Butyrolactones Bearing Two Vicinal Stereocenters Enabled by Synergistic Copper and Iridium Catalysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(47), P. 24930 - 24940

Published: Oct. 11, 2021

By virtue of a fundamentally new reaction model azomethine ylide serving as two-atom synthon, we present the first example stereodivergent preparation γ-butyrolactones via synergistic Cu/Ir-catalyzed asymmetric cascade allylation/lactonization, and all four stereoisomers bearing two vicinal stereocenters are accessible with excellent diastereoselective enantioselective control. The chiral IrIII -π-allyl intermediate was separated characterized to understand origin regio- stereoselectivity initial C-C bond formation process. Control experiments shed some light on catalyst/substrate catalyst/catalyst interactions in this dual catalytic system rationalize related kinetic/dynamic kinetic resolution process different catalyst combinations. enantioenriched γ-butyrolactone products were converted into an array structurally complex molecules organocatalysts that otherwise inaccessible.

Language: Английский

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Dispersion and Steric Effects on Enantio-/Diastereoselectivities in Synergistic Dual Transition-Metal Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(4), P. 1971 - 1985

Published: Jan. 20, 2022

Comprehensive computational studies were carried out to explore the mechanisms of enantioselective Cu/Pd and stereodivergent Cu/Ir dual-catalytic syntheses α,α-disubstituted α-amino acids (α-AAs). A chiral copper azomethine ylide undergoes facile α-allylation with racemic π-allylpalladium species or stereopure π-allyliridium complex stereoconvergently stereodivergently furnish single/double stereocenters, respectively. Stereoselectivity at α-center is controlled by facial selectivity respect prochiral nucleophile. Despite apparently similar transition-state assemblies, models distortion/interaction analyses disclose versatile modes stereoinduction wherein can face-selectively intercept metal−π-allyl intermediates utilizing attractive dispersion interactions and/or sterically caused distortions. Generation β-stereocenter in system relies on a stereospecifically generated allyliridium electronically branched-to-linear selectivity, while dual yields linear monochiral product due steric factors π–π stacking interactions. The demonstrate molecular level how ligand-encoded information transferred α-/β-sites resulting α-AAs mode regio-/stereoselection altered differences transition-metal-stabilized coupling partners. To facilitate stereoselective catalysis, suite analytical tools extract controlling for asymmetric induction demonstrated.

Language: Английский

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High-order dipolar annulations with metal-containing reactive dipoles

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(10), P. 4146 - 4174

Published: Jan. 1, 2022

The advances on metal-catalysed high-order dipolar annulations were comprehensively summarized in this review. To further exploit the potential of unique annulation strategy, a research outlook was also proposed.

Language: Английский

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Stereodivergent Construction of 1,4‐Nonadjacent Stereocenters via Hydroalkylation of Racemic Allylic Alcohols Enabled by Copper/Ruthenium Relay Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: June 28, 2022

An unprecedented hydroalkylation of racemic allylic alcohols and ketimine esters enabled by Cu/Ru relay catalysis has been developed via merging the ruthenium-catalyzed asymmetric borrowing-hydrogen reaction with a copper-catalyzed Michael addition in one-pot procedure. The current method enables efficient preparation highly functionalized δ-hydroxyesters bearing 1,4-nonadjacent stereocenters good yields high levels diastereoselectivity excellent enantioselectivity under mild conditions. full complement four stereoisomers products could be readily accessed orthogonal permutations two chiral metal catalysts. work highlights power for stereodivergent construction that were otherwise inaccessible.

Language: Английский

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Synergistic Dual Catalysis in Stereodivergent Synthesis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 3812 - 3844

Published: Feb. 23, 2024

Chiral skeletons with multiple stereogenic centers widely reside in nature and drugs, their relative absolute configuration often determine physiological or pharmacological properties. Stereodivergent synthesis of chiral molecules is not only great significance, but also highly challenging since the formation one diastereomers inherently preferred most asymmetric reactions. dual catalysis, introduced 2013 by Carreira group, perfectly catered to all requirements for full stereoselectivity control given reactions two catalysts are utilized a synergistic way act independently, has now been arguably efficient strategy realize stereodivergent synthesis. This comprehensive review presents an overview development enabled catalysis past ten years, providing readers fundamental attributes as well ability, scope, mechanism, limitations this strategy.

Language: Английский

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Interrupting Associative π–σ–π Isomerization Enables Z-Retentive Asymmetric Tsuji–Trost Reaction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(3), P. 2776 - 2785

Published: Jan. 8, 2025

The asymmetric Tsuji-Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent an E-olefin moiety organic molecules. generally preferential formation of chiral products is believed result from the thermodynamically more stable syn-π-allylpalladium intermediate. rapid associative π-σ-π isomerization makes it challenging synthesize Z-olefin via transient anti-π-allylpalladium Herein, we report a strategy for regulating by tuning steric bulkiness ligands, allylic leaving groups, and counteranions. utilization Pd catalyst derived phosphoramidite ligands interrupts isomerization, enabling highly efficient Z-retentive toward array α-amino acid derivatives bearing motif high yields (up 95%) excellent stereoselectivity 99% ee >19:1 Z/E) with low loading (0.1 mol %). mechanistic insights design reported this work pave way rational developments Tsuji-Trost-type reactions.

Language: Английский

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Diastereodivergent Synthesis of β‐Amino Alcohols by Dual‐Metal‐Catalyzed Coupling of Alkoxyallenes with Aldimine Esters

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(12), P. 6545 - 6552

Published: Dec. 4, 2020

Abstract Both syn ‐ and anti ‐β‐amino alcohols are common structural motifs in natural products, drug molecules, chiral ligands catalysts. However, the currently available methods for synthesizing these limited to generate only one diastereoisomer. Therefore, development of a unified method stereoselective access complementary diastereomers would be highly desirable. Herein, we report dual‐metal‐catalyzed diastereodivergent coupling alkoxyallenes with aldimine esters. By carefully selecting two metals appropriate ligands, could synthesize both alcohol high enantioselectivity diastereoselectivity from same set starting materials. Furthermore, stereodivergent syntheses all four stereoisomers β‐amino achieved. We demonstrated synthetic utility this by concisely mycestericins F G.

Language: Английский

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The Discovery of Multifunctional Chiral P Ligands for the Catalytic Construction of Quaternary Carbon/Silicon and Multiple Stereogenic Centers

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 54(2), P. 452 - 470

Published: Dec. 30, 2020

The development of highly effective chiral ligands is a key topic in enhancing the catalytic activity and selectivity metal-catalyzed asymmetric synthesis. Traditionally, difficulty ligand synthesis, insufficient accuracy controlling stereoselectivity, poor universality systems often become obstacles this field. Using concept nonequivalent coordination to metal, our group has designed synthesized series new catalysts access various carbon/silicon and/or multiple stereogenic centers containing products with excellent chemo-, diastereo-, enantioselectivity.In Account, we summarize phosphine that have been developed laboratory. These exhibited good performance transition-metal-catalyzed enantioselective construction quaternary centers. In first section, notable examples design synthesis by non-covalent interaction-based multisite activation are described. integrations axial chirality, atom-centered anions multifunctional groups into single scaffold individually highlighted, as represented Ar-BINMOLs their derivative ligands, HZNU-Phos, Fei-Phos, Xing-Phos. second, third, fourth sections, carbon stereocenters, centers, silicon using newly summarized. sections refer detailed reaction information chiral-ligand-controlled catalysis based on activation. Accordingly, wide array transition metal main-group applied heterocycles, amino acid derivatives, cyclic ketones, alkenes, organosilicon compounds bearing one five stereocenters.This Account shows model ligand-controlled exhibits stereocontrol efficiency, especially stereodivergent atom-economical fashion. Furthermore, brief mechanistic understanding origin enantioselectivity from catalyst could inspire further enhancement catalysis.

Language: Английский

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Advances in Catalytic Asymmetric Reactions Using 2-Indolylmethanols as Platform Molecules

Chinese Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 42(10), P. 3351 - 3351

Published: Jan. 1, 2022

Indole-based chiral heterocycles constitute a class of important heterocyclic compounds that are found in numerous natural products, pharmaceuticals, pesticide, and functional materials.The efficient highly enantioselective synthesis indole derivatives has become one the most issues organic chemistry.Due to simple reactivity traditional indoles, their involved catalytic asymmetric reactions very limited, resulting limited types constructed indole-based frameworks.To solve these challenging issues, chemists devised strategy introducing groups ring, so as obtain series functionalized derivatives, namely platform molecules, building blocks for constructing indole-related frameworks.Among them, 2-indolylmethanols which were designed on consideration introduction hydroxymethyl group C2-position ring would change reactive site ring.This molecules can act either electrophiles or nucleophiles, multi-carbon reactions.Therefore, design development have provided new derivatives.The advances using summarized, will open window designing application molecules.

Language: Английский

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