Enantio- and Diastereodivergent N-Heterocyclic Carbene/Nickel Dual-Catalyzed Umpolung Propargylic Substitutions of Enals DOI
Lingzi Peng, Mingxu Wang, Jianming Huang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(51), P. 28085 - 28095

Published: Nov. 30, 2023

The creation of full stereoisomers an organic compound comprising multiple contiguous stereocenters with simultaneous control over both relative and absolute configurations remains a significant challenge in synthetic chemistry. Using cooperative catalysis strategy, we established N-heterocyclic carbene/nickel-catalyzed enantio- diastereodivergent propargylation reaction to access 3,3'-disubstituted oxindoles, enabling the incorporation internal alkyne functionality introduction single quaternary or vicinal quaternary/tertiary stereogenic center. By selecting appropriate combination catalyst chirality, all four potential α-quaternary propargylated oxindoles were synthesized predictable precise way remarkable yields, diastereoselectivities, enantioselectivities from identical starting materials. utility this method was demonstrated concise asymmetric total synthesis (-)-debromoflustramine B (-)-C(β-Me)-debromoflustramine B.

Language: Английский

Bimetallic Catalysis in Stereodivergent Synthesis DOI
Xiaohong Huo, Guanlin Li, Xi Wang

et al.

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

Citations

139
Stereodivergent total synthesis of rocaglaol initiated by synergistic dual-metal-catalyzed asymmetric allylation of benzofuran-3(2H)-one DOI Creative Commons
Yang Xu,

Hongkai Wang,

Zhuang Yang

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(7), P. 2011 - 2022

Published: May 2, 2022

Language: Английский

Citations

87
Synergizing palladium with Lewis base catalysis for stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates DOI Creative Commons
Qinglong Zhang, Minghui Zhu, Weiwei Zi

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(10), P. 2784 - 2796

Published: Aug. 17, 2022

Language: Английский

Citations

72
Stereodivergent Construction of 1,4‐Nonadjacent Stereocenters via Hydroalkylation of Racemic Allylic Alcohols Enabled by Copper/Ruthenium Relay Catalysis DOI
Xin Chang, Xiang Cheng,

Xue‐Tao Liu

et al.

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

Citations

71
Diastereodivergent Desymmetric Annulation to Access Spirooxindoles: Chemical Probes for Mitosis DOI

Yu‐Hua Wen,

Fengrui Yang, Shuai Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 4199 - 4207

Published: Feb. 13, 2023

Spirooxindoles have emerged as promising architectures for engineering biologically active compounds. The diastereodivergent construction of unique scaffolds this type with full control continuous chiral centers including an all-carbon quaternary stereogenic center is yet to be developed. Here, we report unprecedented desymmetric [3 + 3] annulation oxabicyclic alkenes enals enabled by N-heterocyclic carbene (NHC)/Rh cooperative catalysis, leading a series enantiomerically enriched spirooxindole lactones excellent enantioselectivities (up >99% ee) and diastereoselectivities >95:5 dr). combined catalyst system comprises rhodium complex that controls the configuration at electrophilic carbon NHC nucleophilic oxindole-containing carbon; thus, four stereoisomers products can readily obtained simply switching configurations two catalysts. Transformations spirooxindoles delivered synthetically useful Importantly, those arrested mammalian cells in mitosis exhibited potent antiproliferative activities against HeLa cells. Significantly, both absolute relative exert prominent effects on bioactivities, underscoring great importance catalytic asymmetric synthesis beyond creating tools exploration structure–activity relationships.

Language: Английский

Citations

47
Synergistic Dual Catalysis in Stereodivergent Synthesis DOI
Liang Wei, Cong Fu,

Zuo-Fei Wang

et al.

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

Citations

31
Catalytic Asymmetric Diastereodivergent Synthesis of 2-Alkenylindoles Bearing both Axial and Central Chirality DOI Creative Commons
Shuang Yang,

Jia-Bo Huang,

Dahua Wang

et al.

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(5), P. 208 - 220

Published: April 23, 2024

The catalytic asymmetric diastereodivergent synthesis of axially chiral 2-alkenylindoles was established via phosphoric acid-catalyzed addition reactions C3-unsubstituted with

Language: Английский

Citations

16
Diastereodivergent Aldol‐Type Coupling of Alkoxyallenes with Pentafluorophenyl Esters Enabled by Synergistic Palladium/Chiral Lewis Base Catalysis DOI
Minghui Zhu, Peixin Wang, Qinglong Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 17, 2022

As a fundamental and synthetically useful C-C bond formation reaction, the aldol reaction is one of most versatile transformations in organic synthesis. However, despite extensive research on asymmetric versions unified method for stereoselective access to complementary syn anti diastereomeric products remains be developed. In this study, we developed synergistic palladium/chiral Lewis base system that overcomes inherent diastereoselectivity bias reactions and, as result, allowed us achieve first diastereodivergent coupling alkoxyallenes with pentafluorophenol esters. Computational studies suggest mechanism involving an intermolecular protonative hydropalladation pathway rather than palladium-hydride migratory insertion pathway. The origin stereochemistry catalysis rationalized by DFT calculations.

Language: Английский

Citations

64
Dual Catalysis in Organic Synthesis: Current Challenges and New Trends DOI
Chandi C. Malakar, Luca Dell’Amico, Wanbin Zhang

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 26(1)

Published: Dec. 9, 2022

Abstract Dual catalysis is one of the most powerful strategies for development chemical reactions in organic synthesis. This strategy can be divided into cooperative catalysis, relay and sequential according to actual mode operation communication between catalysts. In recent years, such has been applied a large number studies since it advantages of: 1) increasing reactivity enabling challenging transformations; 2) offering way controlling stereoselectivity asymmetric reactions, which traditional catalytic systems; 3) catalyze stereodivergent synthesis molecules bearing or more stereocenters from same starting materials. Perspective, intends introduce reader EurJOC special collection on Catalysis , aims summarize different categories dual demonstrate their benefits constructing new bonds selective manner. Finally, current challenges trends will also presented.

Language: Английский

Citations

56
Asymmetric transformations enabled by synergistic dual transition-metal catalysis DOI Creative Commons
Liang Wei, Chun‐Jiang Wang

Chem Catalysis, Journal Year: 2022, Volume and Issue: 3(1), P. 100455 - 100455

Published: Nov. 17, 2022

Language: Английский

Citations

55