Asymmetric Bimetallic Catalysis Enabled Alkenyl Z/E Mutual Isomerization DOI
Guanlin Li,

Zheyuan Lai,

Zheng En

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Июнь 5, 2025

Olefins are fundamental functional groups present in numerous molecules, and the geometrical configuration of C═C bonds often plays a critical role determining properties these compounds. Alkenyl isomerization is, principle, one most efficient approaches for accessing stereodefined olefins. While some progress has been made achieving unidirectional Z → E or conversion via olefin isomerization, there remains strong demand controllable, bidirectional bonds. Herein, we method Z/E mutual alkenyl by using Pd/Cu catalytic system. This process involves Pd-mediated π-σ-π interconversion followed selective trapping π-allyl-Pd intermediates with N-metalated azomethine ylides generated chiral Cu-catalyst. The reaction enables synthesis non-natural amino acid derivatives bearing Z- E-alkenyl an enantio- Z/E-divergent manner, yields up to 92%, > 20:1 E/Z, >99% ee. Furthermore, is scalable gram quantities, resulting products can be transformed into valuable molecules adorned groups. Computational studies show that bimetallic system better distinguishes among eight stereoisomers than monometallic system, which results exceptional Z/E-selectivity products. offers robust protocol synthesizing E-trisubstituted olefins motif utilizing readily available Z/E-mixture substrates.

Язык: Английский

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

Zuo-Fei Wang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 3812 - 3844

Опубликована: Фев. 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.

Язык: Английский

Процитировано

36
Synergistic Pd/Cu-Catalyzed 1,5-Double Chiral Inductions DOI
Jiacheng Zhang, Yicong Luo, Zheng En

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9241 - 9251

Опубликована: Март 19, 2024

Much attention has been focused on the catalytic asymmetric creation of single chiral centers or two adjacent stereocenters. However, construction nonadjacent stereocenters is significant importance but challenging because lack remote induction models. Herein, based a C═C bond relay strategy, we report synergistic Pd/Cu-catalyzed 1,5-double model. All four stereoisomers target products bearing 1,5-nonadjacent involving both allenyl axial and central chirality could be obtained divergently by simply changing combination catalysts with different configurations. Control experiments DFT calculations reveal novel mechanism 1,5-oxidative addition, contra-thermodynamic η3-allyl palladium shift, conjugate nucleophilic substitution, which play crucial roles in control reactivity, regio-, enantio-, diastereoselectivity. It expected that this strategy may provide general protocol for synthesis structural motifs distant

Язык: Английский

Процитировано

19
Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols DOI

Baihui Gong,

Qing‐Bin Lu,

R. Li-jiun Sun

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2351 - 2358

Опубликована: Янв. 24, 2025

Язык: Английский

Процитировано

3
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

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(31)

Опубликована: Июнь 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.

Язык: Английский

Процитировано

27
Copper/Ruthenium Relay Catalysis for Stereodivergent Access to δ‐Hydroxy α‐Amino Acids and Small Peptides DOI
Cong Fu, Ling He, Xin Chang

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 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.

Язык: Английский

Процитировано

27
Synergistic Palladium/Copper‐Catalyzed 1,4‐Difunctionalization of 1,3‐Dienes for Stereodivergent Construction of 1,5‐Nonadjacent Stereocenters DOI
Hongfa Wang, Ruiyuan Zhang, Weiwei Zi

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 21, 2024

Abstract The construction of two distal stereocenters through a single catalytic process is great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation 1,3‐ or 1,4‐stereocenters, the more challenged 1,5‐nonadjacent have never been achieved fashion. Herein we describe synergistic palladium/copper catalysis for 1,4‐difunctionalization reactions 1,3‐dienes, providing access to quaternary stereocenters. Because each catalysts separately controlled one newly formed stereocenters, synthesis all four diastereomers products could readily be simply by choosing an appropriate combination chiral catalysts. Experimental and computational studies supported mechanism involving Heck/Tsuji–Trost cascade reaction, origins stereoselectivity were elucidated.

Язык: Английский

Процитировано

14
Stereodivergent access to non-natural α-amino acids via enantio- and Z / E -selective catalysis DOI
Panpan Li, Zheng En, Guanlin Li

и другие.

Science, Год журнала: 2024, Номер 385(6712), С. 972 - 979

Опубликована: Авг. 29, 2024

The precise control of

Язык: Английский

Процитировано

14
Enantioselective Tsuji‐Trost α‐Fluoroallylation of Amino Acid Esters with Gem‐Difluorinated Cyclopropanes DOI
Zheng Su,

Binhong Tan,

Hui He

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Фев. 27, 2024

A novel enantioselective Tsuji-Trost-type cross coupling reaction between gem-difluorinated cyclopropanes and N-unprotected amino acid esters enabled by synergistic Pd/Ni/chiral aldehyde catalysis is presented herein. This transformation streamlined the diversity-oriented synthesis (DOS) of optically active α-quaternary α-amino bearing a linear 2-fluoroallylic motif, which served as an appealing platform for construction other valuable enantioenriched compounds. The key intermediates were confirmed HRMS detection, while DFT calculations revealed that excellent enantioselectivity was attributed to stabilizing non-covalent interactions Pd(II)-π-fluoroallyl species Ni(II)-Schiff base complex.

Язык: Английский

Процитировано

12
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

и другие.

Advanced Science, Год журнала: 2024, Номер 11(23)

Опубликована: Март 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.

Язык: Английский

Процитировано

12
Stereodivergent Construction of 1,5/1,7‐Nonadjacent Tetrasubstituted Stereocenters Enabled by Pd/Cu‐Cocatalyzed Asymmetric Heck Cascade Reaction DOI
Panpan Li,

Zijiao Liu,

Xiaohong Huo

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Май 16, 2024

Abstract The construction of chiral motifs containing nonadjacent stereocenters in an enantio‐ and diastereoselective manner has long been a challenging task synthetic chemistry, especially with respect to their stereodivergent synthesis. Herein, we describe protocol that enables the 1,5/1,7‐nonadjacent tetrasubstituted through Pd/Cu‐cocatalyzed Heck cascade reaction. Notably, C=C bond relay strategy involving shift π‐allyl palladium intermediate was successfully applied asymmetric 1,7‐nonadjacent stereocenters. current method allows for efficient preparation molecules bearing two privileged scaffolds, oxindoles non‐natural α‐amino acids, good functional group tolerance. full complement four stereoisomers products could be readily accessed by simple combination metal catalysts different enantiomers.

Язык: Английский

Процитировано

11