Design and Synthesis of Sulfur-Containing Tetradentate Ligands for Ir-Catalyzed Asymmetric Hydrogenation of Ketones DOI
Yuanzheng Wang, Yanan Duan, Gen‐Qiang Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 30, 2024

Developing highly active and enantioselective ligands for the asymmetric hydrogenation of ketones has consistently attracted significant attention from scientists. A series novel tetradentate sulfur-containing ligands, termed as f-thiophamidol, were successfully designed synthesized which exhibited excellent performance in simple (up to 99% yield, ee) α-substituted β-keto sulfonamides ee, 99:1 dr). The subsequent successful gram-scale experiments with high TON demonstrated immense potential application value this system synthesizing drug molecules.

Language: Английский

The importance of alkali cations in manganese-catalyzed enantioselective transfer hydrogenation of ketones: An insight into the effect of “NH” and “C N” groups in ligands DOI
Zechen Wang, Yuanyuan Wang,

Quanming Lyu

et al.

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115998 - 115998

Published: Feb. 1, 2025

Language: Английский

Citations

1
Photoinduced Copper-Catalyzed Radical Mizoroki–Heck Reaction with Unactivated Alkyl Iodide DOI
Yongjie Xu,

Hang Luo,

Dan Hu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Herein, we present a method for copper-catalyzed photoinduced radical Mizoroki-Heck (M-H) reactions utilizing unactivated alkyl iodides and styrene. This approach enables the smooth generation of (E)-olefin products with good functional group tolerance, demonstrating broad applicability. The mechanism involves in situ formation copper complex that binds to iodide, leading fragmentation under visible-light irradiation. process generates radicals persistent copper(II) complex, both which are crucial subsequent olefin formation. Primary mechanistic studies support cleavage C(sp3)-I bond via an inner-sphere electron transfer (ISET) involving excited Cu(I) associated iodide. Finally, M-H product occurs base-assisted β-H elimination process.

Language: Английский

Citations

0
Amplifying the Reactivity of Anionic Mn(I)–H Catalysts via the Cation Effect: Mechanistic Investigation and Application to the Hydrogenation of α-Trisubstituted Carboxylic Esters DOI
Haobo Yang, Shihan Liu, Hao Dong

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Despite significant advancements in ester hydrogenation using homogeneous metal catalysts over the past two decades, catalytic of sterically hindered α-trisubstituted carboxylic esters remains a formidable challenge. Herein, we present class imidazole-based NNP-pincer manganese (Mn) capable efficiently hydrogenating to their corresponding β-trisubstituted primary alcohols, which are widely applied pharmaceutical and fine-chemical industry. Under conditions, imidazole moiety is deprotonated by tBuOK generate highly reactive anionic Mn-H species with potassium countercation. Mechanistic studies reveal that cation this intermediate interacts synergistically substrate's carbonyl group alkoxide during hydrogen activation. This effect significantly lowers energy barriers for both hydride transfer heterolytic H2 cleavage, thereby enhancing activity. Leveraging potent catalyst, achieved diverse array carboxylates (80 examples) under mild conditions.

Language: Английский

Citations

0
Dynamic Kinetic Resolution of β-Cyano α-Ketoesters via Asymmetric Transfer Hydrogenation DOI

Ruiyu Hu,

Fangyuan Wang,

Fan Pan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7457 - 7462

Published: Aug. 26, 2024

An efficient rhodium-catalyzed asymmetric transfer hydrogenation of β-cyano α-ketoesters via dynamic kinetic resolution has been developed. Despite the challenge posed by multiple functional groups, reaction proceeded smoothly under mild conditions, generating versatile synthons with two adjacent stereocenters in high yields excellent enantio- and diastereoselectivities. Furthermore, power this strategy is highlighted scale-up follow-up synthesis cytoxazone paclitaxel intermediates.

Language: Английский

Citations

2
Ir-catalyzed chemo- and enantioselective hydrogenation of enyne-conjugated ketones DOI

Xuejuan Zheng,

Fanping Huang,

Jianfei Yu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(21), P. 6207 - 6212

Published: Jan. 1, 2024

We herein report an efficient asymmetric hydrogenation of β-alkynyl α,β-unsaturated ketones by using Ir/f-phamidol as a catalyst under mild conditions, providing the corresponding chiral alcohols in up to 99% yield and ee.

Language: Английский

Citations

0
Ferrocene-based P,P,N,N,O-ligands for ruthenium-catalyzed enantioselective hydrogenation DOI
Lei Xu, Gen‐Qiang Chen, Xumu Zhang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A new type of ferrocenyl P,P,N,N,O-ligand has been developed through a one-step transformation. This represents rare example ligand containing both chiral bisphosphine and diamine groups suitable for ruthenium-catalyzed asymmetric hydrogenation. Its ruthenium complex can be directly prepared by stirring the [Ru(benzene)Cl

Language: Английский

Citations

0
Highly Enantioselective Hydrogenation of Unsymmetrical Benzophenones via Iridium–f-phamidol Catalysis DOI
Fanping Huang, Qiwei Lang, Gen‐Qiang Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6159 - 6163

Published: July 18, 2024

A sequence of

Language: Английский

Citations

0
Design and Synthesis of Sulfur-Containing Tetradentate Ligands for Ir-Catalyzed Asymmetric Hydrogenation of Ketones DOI
Yuanzheng Wang, Yanan Duan, Gen‐Qiang Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 30, 2024

Developing highly active and enantioselective ligands for the asymmetric hydrogenation of ketones has consistently attracted significant attention from scientists. A series novel tetradentate sulfur-containing ligands, termed as f-thiophamidol, were successfully designed synthesized which exhibited excellent performance in simple (up to 99% yield, ee) α-substituted β-keto sulfonamides ee, 99:1 dr). The subsequent successful gram-scale experiments with high TON demonstrated immense potential application value this system synthesizing drug molecules.

Language: Английский

Citations

0