Synergistic Homogeneous Asymmetric Cu Catalysis with Pd Nanoparticle Catalysis in Stereoselective Coupling of Alkynes with Aldimine Esters DOI Creative Commons
Yong Liu, Hongda Chen, Xiaoming Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 2, 2024

Understanding the nature of a transition-metal-catalyzed process, including catalyst evolution and real active species, is rather challenging yet great importance for rational design development novel catalysts, this even more difficult bimetallic catalytic system. Pd(0)/carboxylic acid combined system-catalyzed allylic alkylation reaction alkynes has been used as an atom-economical protocol synthesis products. However, asymmetric version still limited, in-depth understanding Pd species elusive. Herein we report enantioselective coupling between readily available aldimine esters using synergistic Cu/Pd system, affording diverse set α-quaternary allyl amino ester derivatives in good yields with excellent enantioselectivities. Mechanistic studies indicated that it most likely molecular Cu catalysis nanoparticle catalysis. The precursor transformed to soluble nanoparticles

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
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
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
Stereodivergent Construction of Csp3−Csp3Bonds Bearing Vicinal Stereocenters by Synergistic Palladium and Phase‐Transfer Catalysis DOI

Jingqiang Han,

Rixin Liu,

Zitong Lin

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Nov. 16, 2022

Abstract Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation Csp 3 −Csp bonds bearing vicinal stereocenters. Despite many successes that have been achieved in this field, coupling reactions involving stabilized nucleophiles remain challenging because competing single‐catalysis pathway. Herein, we report a synergistic palladium/phase‐transfer catalyst system enables diastereodivergent 1,3‐dienes with nucleophile oxindoles. Both syn and anti products, quaternary tertiary stereocenters, could be selectively produced good yields high enantio‐ diastereoselectivities. Non‐covalent activation via chiral ion pair biphasic is crucial success factor achieving diastereodivergence.

Language: Английский

Citations

40
Enantio‐ and Diastereoselective Synthesis of Chiral Tetrasubstituted α‐Amino Allenoates Bearing a Vicinal All‐Carbon Quaternary Stereocenter with Dual‐Copper‐Catalysis DOI

Cheng Sheng,

Zheng Ling, Junzhe Xiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 1, 2023

The skeletons of chiral tetrasubstituted allenes bearing a vicinal all-carbon quaternary stereocenter are importance but still challenging to synthesize. Herein, we report enantio- and diastereoselective γ-additions 1-alkynyl ketimines with dual-copper-catalysis under mild conditions, affording α-amino allenoates in high yields (up 99 % yield) excellent enantioselectivities ee) diastereoselectivities >20 : 1 dr). Importantly, the stereodivergent synthesis products was realized by asymmetric γ-addition reaction Grignard reagent promoted epimerization. Moreover, dual-copper-catalyzed reactions were smoothly applied gram-scale adopted introduce allenyl moieties into bioactive molecules. Mechanistic experiments density functional theory (DFT) calculations demonstrated that catalyzed double copper catalysts.

Language: Английский

Citations

27
Synergistic Catalysis Involving Palladium for Stereodivergent Csp3–Csp3 Coupling Reactions DOI
Hongfa Wang, Qinglong Zhang, Weiwei Zi

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 31, 2024

ConspectusTransition-metal-catalyzed coupling reactions of dienes (such as 1,3-dienes, alkoxyallenes, and aminoallenes) with carbon nucleophiles have proven to be a highly effective method for creating Csp3–Csp3 bonds. These perfect atom economy typically occur under mild reaction conditions. By using chiral metal complexes catalysts, it is possible create enantioenriched molecules bearing allylic stereocenters high enantioselectivities. However, challenges arise when bonds two vicinal are constructed through this type reaction. Due the inherent diastereoselectivities, only kinetically favored diastereoisomers (either syn- or anti-product) usually obtained transition-metal catalyst system. Achieving complementary stereoisomers selectivity, which require complete control both absolute relative configurations multiple centers in single chemical transformation, impossible.Over past decade, significant advancements been made stereodivergent synthesis. Notably, iridium-related synergistic catalysis has rapidly developed alkylation reactions. these systems were limited alcohol derivatives electrophilic partners. Finding ways extend use other types crucial issue that needs addressed.In 2019, we reported first palladium-mediated system between 1,3-dienes aldimine esters. Lately, strategy successful accessing diverse substrate patterns. In Account, will summarize our laboratory's efforts developing range palladium-involved dienes. We discovered several systems, including Pd/Cu(Ag), Pd/amine, Pd/Lewis base, Pd/PTC. Additionally, dienes, such aminoallenes, serve suitable partners coupling. processes provide an efficient constructing scaffolds stereocenters. Density functional theory (DFT) calculations performed elucidate mechanism rationalize origins stereochemistry some systems. Finally, synthetic application methods demonstrated concise total synthesis number natural products bioactive molecules. It anticipated increasing chemists join research on contribute more elegant examples area. believe future development further push boundary asymmetric find innovative applications soon synthesizing complex

Language: Английский

Citations

8
Enantioselective Three‐Component Photochemical 1,4‐Bisalkylation of 1,3‐Butadiene with Pd/Cu Catalysis DOI
Huimin Yu, Qinglong Zhang, Weiwei Zi

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: June 27, 2022

Catalysis by excited-state palladium has emerged as an active area of research, but controlling the enantioselectivity remains a challenge. Herein, we report use synergistic Pd/Cu catalysis to accomplish first three-component photochemical 1,4-bisalkylation reactions 1,3-butadiene. Consequently, α-amino acid esters bearing quaternary stereocenters were expeditiously synthesized from three simple starting materials: alkyl bromide, butadiene, and aldimine ester. Experimental computational investigation reaction mechanism confirmed radical pathway involving species. The stereochemistry is mainly controlled chiral Cu catalyst.

Language: Английский

Citations

34
Stereodivergent dehydrative allylation of β-keto esters using a Ru/Pd synergistic catalyst DOI Creative Commons

Thien Phuc Le,

Shinji Tanaka, Masahiro Yoshimura

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Oct. 12, 2022

Abstract α-Alkylation of a β-keto ester is frequently used reaction for carbon–carbon bond formation. However, extension to stereoselective remains significant challenge, because the product easily racemizes under acidic or basic conditions. Here, we report hybrid system consisting Pd and Ru complexes that catalyzes asymmetric dehydrative condensation between cinnamyl-type allylic alcohols esters. α-Non-substituted can be allylated afford an α-mono-substituted with high regio-, diastereo-, enantioselectivity. No epimerization occurs owing nearly neutral conditions, which achieved by rapid proton transfer from Pd-enolate formation π-allyl complex Four diastereomers synthesized on demand changing stereochemistry complex. Eight stereoisomers three adjacent stereogenic centers employing diastereoselective reduction ketone in products. The formal synthesis (+)-pancratistatin demonstrates utility reaction.

Language: Английский

Citations

30
Enantioselective and stereodivergent hydromonofluoroalkylation of conjugated and remote dienes DOI

Qi-Ying Liao,

Chao Ma, Yuchao Wang

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(12), P. 108371 - 108371

Published: March 23, 2023

Language: Английский

Citations

22
Bimetallic Ru/Ru‐Catalyzed Asymmetric One‐Pot Sequential Hydrogenations for the Stereodivergent Synthesis of Chiral Lactones DOI Creative Commons

Jingli He,

Zhaodi Li,

Ruhui Li

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(23)

Published: March 21, 2024

Abstract Asymmetric sequential hydrogenations of α ‐methylene γ ‐ or δ ‐keto carboxylic acids are established in one‐pot using a bimetallic Ru/Ru catalyst system, achieving the stereodivergent synthesis all four stereoisomers both chiral and ‐lactones with two non‐vicinal carbon stereocenters high yields (up to 99%) excellent stereoselectivities >99% ee >20:1 dr). The compatibility Ru systems is investigated detail, it found that basicity reaction system plays key role hydrogenation processes. protocol can be performed on gram‐scale low loading 11000 S/C) resulting products allow for many transformations, particularly several intermediates useful preparation drugs natural products.

Language: Английский

Citations

8