Asymmetric Hydroxymethylative Etherification of 1,3-Dienes with Isatins and Alcohols via Pd(0)-π-Lewis Base Catalysis DOI

Bo Jiang,

Haotian Wang, Zhichao Chen

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(2), P. 628 - 636

Published: Dec. 28, 2023

Although the asymmetric hydroalkoxylation of 1,3-dienes has been achieved recently, development a modular and mechanistically distinct strategy for concurrently introducing an alkoxyl group another chiral moiety into remains to be disclosed. Presented herein is palladium(0)-π-Lewis base-catalyzed hydroxymethylative etherification reaction 1,3-dienes, isatins, aliphatic alcohols, proceeding through cascade vinylogous addition allylic sequence. This three-component exhibits broad substrate scope good functionality tolerance under mild catalytic conditions, generally furnishing structurally diverse 1,3-diol derivatives bearing two stereogenic centers with moderate-to-high levels diastereo- enantioselectivity, which can further converted valuable frameworks higher molecular complexity. In addition, few control experiments were conducted elucidate process.

Language: Английский

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis DOI
Tsuneo Imamoto

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

Citations

41
Palladium(0) π-Lewis Base Catalysis: Concept and Development DOI
Zhichao Chen, Qin Ouyang, Wei Du

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6422 - 6437

Published: March 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.

Language: Английский

Citations

14
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

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6936 - 6946

Published: Feb. 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.

Language: Английский

Citations

6
Catalysis and Synthesis Enabled by P-Chiral Dihydrobenzooxaphosphole Ligands DOI
Zhen Cao, Dongyang He, Wenjun Tang

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 949 - 977

Published: April 8, 2024

P-Chiral phosphorus ligands received little attention in organic chemistry until Knowles made his landmark contribution asymmetric hydrogenation by developing the P-chiral CAMP and DIPAMP. The development of accelerated end last century with advent some highly efficient renowned for hydrogenation, including BisP*, TangPhos, QuinoxP*, DuanPhos, et al. However, most reported were air-sensitive, difficult to make, or lacked structural modularity, hampering their availability applicability. sterically electronically tunable is particularly desirable. Over past decade, a family hindered, electron-rich, structurally tunable, air-stable dihydrobenzooxaphosphole emerged that proved be versatile various transformations. 5 years witnessed an increasing number studies related these discovery unprecedented catalytic properties This review highlights unique catalysis applications synthesis natural products therapeutic agents.

Language: Английский

Citations

5
Facile Synthesis of Quinoline-Substituted 3-Hydroxy-2-oxindoles and 3-Amino-2-oxindoles via a Palladium-Catalyzed Cascade Intramolecular Cyclization/Intermolecular Nucleophilic Addition Reaction DOI

Huawei Lin,

Xinyan Hu, Bing Han

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3413 - 3418

Published: Feb. 20, 2024

An efficient cascade intramolecular cyclization/intermolecular nucleophilic addition reaction of allenyl benzoxazinone with isatin or isatin-derived ketimine has been established by using Pd0-π-Lewis base catalysis. A series 3-hydroxy-2-oxindoles and 3-amino-2-oxindoles quaternary carbon atoms at the C3 position were synthesized in good yields under mild conditions through this protocol.

Language: Английский

Citations

4
Chiral phosphoramidite ligand-modulated palladium auto-tandem catalysis for asymmetric dehydrogenative dienylation of imines with α-alkenes DOI Creative Commons
Zhong‐Sheng Nong, Hui Qian, Ying‐Chun Chen

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

Language: Английский

Citations

0
Functional-Group-Directed Regiodivergent (3 + 2) Annulations of Electronically Distinct 1,3-Dienes and 2-Formyl Arylboronic Acids DOI
Shuyuan Liang,

Tianying Zhang,

Zhichao Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(7), P. 1483 - 1488

Published: Feb. 12, 2024

Presented herein is a palladium-catalyzed asymmetric (3 + 2) annulation reaction between 1,3-dienes and 2-formylarylboronic acids, proceeding in cascade vinylogous addition Suzuki coupling process. Both electron-neutral electron-deficient are compatible under similar catalytic conditions, distinct regioselectivity observed via functional-group control of 1,3-diene substrates. A collection 1-indanols with dense functionalities constructed stereoselectively.

Language: Английский

Citations

3
Palladium(0) and Brønsted Acid Co‐catalyzed Enantioselective Hydro‐Cyclization of 2,4‐Dienyl Hydrazones and Oximes DOI Open Access
Yufan Li,

Wu-Tao Gui,

Fu Pi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: Aug. 6, 2024

Abstract The transition metal‐catalyzed asymmetric hydro‐functionalization of 1,3‐dienes has been well explored, but most reactions focus on electron‐neutral substrates in an intermolecular manner. Here we first demonstrate that readily available 2,4‐dienyl hydrazones and oximes can be efficiently utilized the hydro‐cyclization reaction under co‐catalysis a Brønsted acid chiral palladium complex, furnishing multifunctional dihydropyrazones dihydroisoxazoles, respectively. Diverse substitution patterns for both types electron‐deficient diene compounds are tolerated, corresponding heterocycles were generally constructed with moderate to excellent enantioselectivity, which elaborated access products higher molecular complexity diversity. Control experiments density functional theory calculations support α‐regioselective protonation dienyl by concurrent π‐Lewis base activation Pd 0 complex is energetically favoured formation active π‐allylpalladium intermediates, outer‐sphere allylic amination or etherification mode adopted deliver observed cyclized enantioselectively.

Language: Английский

Citations

3
Catalyst-free racemic and H2O/CPA-catalyzed asymmetric regio-reversed domino processes of triketone enones with azlactones DOI

Yun-Dong Fu,

Xiang Gao, Shi‐Kun Jia

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(14), P. 5692 - 5697

Published: Jan. 1, 2023

The first regio-reversed domino processes of triketone enones with azlactones are established leading to the formation a variety bicyclic furofurans bearing vicinal quaternary carbons in good excellent yields.

Language: Английский

Citations

8
Asymmetric construction of enantioenriched furo[2,3-b]pyridines through sequential gold, palladium/phosphoric acid catalysis DOI
Ke Xie, Guoqing Zhang,

Bao-Rui Kong

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 3900 - 3905

Published: Jan. 1, 2024

A multi-catalytic system combining gold, palladium and phosphoric acid was applied for asymmetric assembly of ynamides carbonate 4-hydroxy-2-cyclopentenone, furnishing furo[2,3- b ]pyridines in high yields stereoselectivities.

Language: Английский

Citations

2