Pd-Catalyzed Asymmetric Allylic Substitution Cascade via Desymmetrization for the Construction of Chiral Polyheterocycles DOI Creative Commons

Xuezhen Kou,

Yongjin Xu, Siqi Dong

и другие.

Pharmaceutical Fronts, Год журнала: 2024, Номер 06(03), С. e237 - e251

Опубликована: Авг. 6, 2024

Chiral polyheterocycles represent an important class of compounds because their prevalence in bioactive natural products and chiral drugs. Pd-catalyzed allylic substitution is a powerful synthetic tool for forming C–C C–X bonds (X = N, O, S, etc.). Naturally, asymmetric cascade reactions that utilize are undoubtedly efficient pathways to construct heterocycles. In this article, we reviewed the via desymmetrization meso-diol diesters cycloolefins, construction derivatives.

Язык: Английский

Palladium(0) π-Lewis Base Catalysis: Concept and Development DOI
Zhichao Chen, Qin Ouyang, Wei Du

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6422 - 6437

Опубликована: Март 1, 2024

The development of a new catalytic strategy plays vital role in modern organic chemistry since it permits bond formation an unprecedented and more efficient manner. Although the application preformed metal complexes as π-base-activated reagents have enabled diverse transformations elegantly, concept by directly utilizing transition metals π-Lewis base catalysts remain underdeveloped, especially field asymmetric catalysis. Here, we outline our perspective on discovery palladium(0) catalyst, which is capable increasing highest occupied molecular orbital (HOMO) energy both electron-neutral electron-deficient 1,3-dienes 1,3-enynes upon flexible η2-complexes formed situ resultant π-backdonation. Thus, fruitful carbon–carbon-forming reactions with electrophiles can be achieved enantioselectively vinylogous addition pattern, conceptually different from classical oxidative cyclization mechanism. Emphasis will given to mechanism elucidation, features, reaction design together further this emerging field.

Язык: Английский

Процитировано

15

Enantioselective Cross-[4 + 2]-Cycloaddition/Decarboxylation of 2-Pyrones by Cooperative Catalysis of the Pd(0)/NHC Complex and Chiral Phosphoric Acid DOI
Mengmeng Xu, Pei‐Pei Xie,

Jun‐Xiong He

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6936 - 6946

Опубликована: Фев. 28, 2024

Here, we describe a cooperative Pd(0)/chiral phosphoric acid catalytic system that allows us to realize the first chemo-, regio-, and enantioselective sequential cross-[4 + 2]-cycloaddition/decarboxylation reaction between 2-pyrones unactivated acyclic 1,3-dienes. The key success of this transformation is utilization an achiral N-heterocyclic carbene (NHC) as ligand newly developed chiral cocatalyst. Experimental investigations computational studies support idea Pd(0)/NHC complex acts π-Lewis base increase nucleophilicity 1,3-dienes via η2 coordination, while simultaneously increases electrophilicity by hydrogen bonding. By synergistic catalysis, 2]-cycloaddition decarboxylation proceeds efficiently, enabling preparation wide range vinyl-substituted 1,3-cyclohexadienes in good yields enantioselectivities. synthetic utility demonstrated transformations product various valuable six-membered carbocycles.

Язык: Английский

Процитировано

6

Carbene-Catalyzed Enantioselective Petasis-Like Alkenylation DOI
Zhipeng Li, Jingyang Zhang, Yani Li

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 2003 - 2013

Опубликована: Янв. 23, 2024

The N-heterocyclic carbene (NHC)-catalyzed enantioselective Petasis-like alkenylation of o-hydroxycinnamaldehydes or hydroxyl-tethered α,β-unsaturated aldehydes with styryl, dienyl, trienyl boronic acids is disclosed. This method involves the addition π-system-containing to NHC-bounded acyl azoliums and allows access divergent assembly β-alkenyl substituted dihydrocoumarin γ- δ-lactones. DFT calculations suggest that an unprecedented zwitterionic intermediate 1,4- 1,5- migration alkenyl groups play a crucial role in reaction. More in-depth studies orbital noncovalent interaction analysis provide more detailed explanations for pathways stereoselectivity control.

Язык: Английский

Процитировано

3

Palladium-Catalyzed Divergent Synthesis from o-Sulfonamido Trifluoroacetophenones and 2-En-4-ynyl Carbonates DOI

Meng-Qi Gan,

Jian‐Xiang Zhu,

Zhichao Chen

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 15, 2025

Here we present a palladium-catalyzed divergent transformative reaction between o-sulfonamido trifluoroacetophenones and 2-en-4-ynyl carbonates. A spectrum of enantioenriched 2,5-dihydrofuran-fused tetrahydroquinolines bearing either (Z)- or (E)-exocyclic double bond are constructed with moderate to high enantioselectivity from 5-aryl-substituted carbonates by tuning palladium sources, while analogous 2,3-dihydrofuran-fused products furnished using 5-alkyl-substituted ones.

Язык: Английский

Процитировано

0

Enantioselective Construction of Polycyclic Chromanes through Organocatalytic Sequential Quintuple Reaction via One‐Pot Step‐Wise Procedure DOI
Jie Wang, Hang Qin, Yali Song

и другие.

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(18), С. 2197 - 2202

Опубликована: Май 14, 2024

Comprehensive Summary An efficient and highly stereoselective synthetic method to access polycyclic chromanes has been achieved through organocatalyzed one‐pot step‐wise reactions involving 2‐hydroxycinnamaldehydes, 2‐aminochalcones, malononitrile as substrates. The underwent a quintuple process by aza‐Michael/Michael/Knoevenagel/oxa‐Michael/aldol‐type reaction in sequence give products bearing 3 new generated rings 5 chiral centers moderate quantitative yields with excellent stereoselectivities. A novel retro‐reaction mechanism was discovered the transformations of products.

Язык: Английский

Процитировано

0

Pd-Catalyzed Asymmetric Allylic Substitution Cascade via Desymmetrization for the Construction of Chiral Polyheterocycles DOI Creative Commons

Xuezhen Kou,

Yongjin Xu, Siqi Dong

и другие.

Pharmaceutical Fronts, Год журнала: 2024, Номер 06(03), С. e237 - e251

Опубликована: Авг. 6, 2024

Chiral polyheterocycles represent an important class of compounds because their prevalence in bioactive natural products and chiral drugs. Pd-catalyzed allylic substitution is a powerful synthetic tool for forming C–C C–X bonds (X = N, O, S, etc.). Naturally, asymmetric cascade reactions that utilize are undoubtedly efficient pathways to construct heterocycles. In this article, we reviewed the via desymmetrization meso-diol diesters cycloolefins, construction derivatives.

Язык: Английский

Процитировано

0