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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Beyond conventional: Role of chiral metal–organic frameworks in asymmetric scenarios

Nano Today, Journal Year: 2024, Volume and Issue: 56, P. 102227 - 102227

Published: March 18, 2024

Language: Английский

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Stereodivergent Construction of 3,3′-Disubstituted Oxindoles via One-Pot Sequential Allylation/Alkylation and Its Application to the Total Synthesis of Trigolute B and D

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

The absolute and relative configurations of bioactive chiral molecules are typically relevant to their biological properties. It is thus highly important desirable construct all possible stereoisomers a lead candidate or given natural compound. Synergistic dual catalysis has been recognized as reliable synthetic strategy for variety predictable stereodivergent transformations. Despite the impressive progress made in this field, carbon-carbon bond-formation reactions involving stabilized nucleophiles remain elusive. Herein, we report an iridium- magnesium-catalyzed one-pot sequential allylic alkylation/nucleophilic alkylation cascade process synthesis four 3,3'-disubstituted oxindoles through three-component reaction. A diverse array products readily prepared with high functional group compatibility good yields excellent diastereo- enantioselectivities. Subsequently, total spirooxindole alkaloid trigolutes B D accomplished concise unified route using same set starting materials.

Language: Английский

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Copper/Ruthenium Relay Catalysis for Stereodivergent Access to δ‐Hydroxy α‐Amino Acids and Small Peptides

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 29, 2023

Abstract An atom‐ and step‐economical redox‐neutral cascade reaction enabled by asymmetric bimetallic relay catalysis merging a ruthenium‐catalyzed borrowing‐hydrogen with copper‐catalyzed Michael addition has been realized. A variety of highly functionalized 2‐amino‐5‐hydroxyvaleric acid esters or peptides bearing 1,4‐non‐adjacent stereogenic centers have prepared in high yields excellent enantio‐ diastereoselectivity. Judicious selection rational modification the Ru catalysts careful tuning conditions played pivotal role stereoselectivity control as well attenuating undesired α‐epimerization, thus enabling full complement all four stereoisomers that were otherwise inaccessible previous work. Concise stereodivergent synthesis key intermediates for biologically important chiral molecules further showcases synthetic utility this methodology.

Language: Английский

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Recent advances in the syntheses and reactions of biologically promising β-lactam derivatives

Tetrahedron, Journal Year: 2025, Volume and Issue: 177, P. 134565 - 134565

Published: Feb. 28, 2025

Language: Английский

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Stereoselective synthesis of β-lactams: recent examples

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(16), P. 3296 - 3306

Published: Jan. 1, 2023

This review covers recent advances towards the stereoselective synthesis of β-lactam derivatives, which is a research topic great interest due to biological activity these molecules.

Language: Английский

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Asymmetric Allylic Substitution Reactions Based on Relay Catalysis

Synthesis, Journal Year: 2024, Volume and Issue: 56(22), P. 3349 - 3364

Published: March 5, 2024

Abstract Transition-metal-catalyzed asymmetric allylic substitution reactions represent a hot research topic in the field of synthesis, with significant progress having been made. Among diverse catalysis systems, relay enables sequential activation multiple steps one pot and rapid construction chiral centers, providing simple powerful platform for organic synthesis. Recently, has successfully applied to reactions, variety challenging transformations have realized. This Short Review summarizes related on based over last decade. 1 Introduction 2 The General Transformation Model 3 Allylation Relays Further Reaction 4 Initial 5 Conclusion Outlook

Language: Английский

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Copper/ruthenium relay catalysis enables 1,6-double chiral inductions with stereodivergence

Chemical Science, Journal Year: 2024, Volume and Issue: 15(26), P. 10135 - 10145

Published: Jan. 1, 2024

A stereodivergent synthesis of chiral ζ-hydroxy amino esters containing 1,6-stereocenters and a unique β,γ-unsaturation was developed through asymmetric Cu/Ru relay catalysis to conduct the borrowing hydrogenation/1,6-Michael addition protocol.

Language: Английский

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Regioselective and asymmetric allylic alkylation of vinyl epoxides for the construction of allylic alcohols via synergistic catalysis

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 542 - 550

Published: Nov. 17, 2023

Language: Английский

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Stereodivergent Ruthenium/Copper Relay Catalysis for Modular Access to δ-Lactones with Two Nonadjacent Carbon Stereocenters

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

The stereodivergent synthesis of δ-lactones, which are prevalent in natural product frameworks, from simple starting materials via a single transformation remains significant challenge. Herein, we report an enantio- and diastereodivergent cascade reaction for the modular chiral δ-lactones bearing two nonadjacent quaternary tertiary carbon stereocenters. This approach employs bimetallic Ru/Cu relay catalysis between allylic alcohols azaaryl acetates. method integrates Ru-catalyzed asymmetric borrowing hydrogen reaction, Cu-catalyzed Michael addition, rapid lactonization into one-pot process, with all catalysts substrates introduced at outset. By orthogonal permutation metal catalysts, precise control over relative absolute configurations newly formed stereocenters is achieved, allowing selective access to stereoisomers δ-lactone products predictable efficient manner.

Language: Английский

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