Highly Active Platinum Catalysts for Nitrile and Cyanohydrin Hydration: Catalyst Design and Ligand Screening via High-Throughput Techniques

Xing, Xiangyou1,2; Xu, Chen1,2; Chen, Bo1; Li, Chengcheng1; Virgil, Scott C.2; Grubbs, Robert H.2

2018-12-19

10.1021/jacs.8b11667

Journal of the American Chemical Society   影响因子和分区

0002-7863

Nitrile hydration provides access to amides that are indispensable to researchers in chemical and pharmaceutical industries. Prohibiting the use of this venerable reaction, however, are (1) the dearth of biphasic catalysts that can effectively hydrate nitriles at ambient temperatures with high turnover numbers and (2) the unsolved challenge of hydrating cyanohydrins. Herein, we report the design of new "donor-acceptor"-type platinum catalysts by precisely arranging electron-rich and electron-deficient ligands trans to one other, thereby enhancing both the nucleophilicity of the hydroxyl group and the electrophilicity of the nitrile group. Leveraging a high-throughput, automated workflow and evaluating a library of bidentate ligands, we have discovered that commercially available, inexpensive DPPF [1,1'-ferrocenendiyl-bis(diphenylphosphine)] provides superior reactivity. The corresponding "donor-acceptor"-type catalyst 2a is readily prepared from (DPPF)PtCl2, PMe2OH, and AgOTf. The enhanced activity of 2a permits the hydration of a wide range of nitriles and cyanohydrins to proceed at 40 degrees C with excellent turnover numbers. Rational reevaluation of the ligand structure has led to the discovery of modified catalyst 2c, harboring the more electron-rich 1,1'-bis[bis(5-methyl-2-furanyl)phosphino] ferrocene ligand, which demonstrates the highest activity toward hydration of nitriles and cyanohydrins at room temperature. Finally, the correlation between the electron-donating ability of the phosphine ligands with catalyst efficiencies of 2a, 2c, 2d, and 2e in the hydration of nitrile 7 are examined, and the results support the "donor-acceptor" hypothesis.

SCI ; EI ; IC ; CCR

英语

NI论文

第一

Shenzhen Nobel Prize Scientists Laboratory Project[C17783101]

Chemistry

Chemistry, Multidisciplinary

WOS:000454383400060

AMER CHEMICAL SOC

20185106268140

Amides ; Catalysts ; Cyanides ; Electrons ; Hydration ; Iron compounds ; Organometallics ; Phosphorus compounds ; Platinum ; Platinum compounds ; Throughput

Precious Metals:547.1 ; Physical Chemistry:801.4 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804

Web of Science

1.Southern Univ Sci & Technol SUSTech, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
2.CALTECH, Div Chem & Chem Engn, Warren & Katharine Schlinger Lab Chem & Chem Engn, Pasadena, CA 91125 USA

Xing, Xiangyou,Xu, Chen,Chen, Bo,et al. Highly Active Platinum Catalysts for Nitrile and Cyanohydrin Hydration: Catalyst Design and Ligand Screening via High-Throughput Techniques[J]. Journal of the American Chemical Society,2018,140(50):17782-17789.

Xing, Xiangyou,Xu, Chen,Chen, Bo,Li, Chengcheng,Virgil, Scott C.,&Grubbs, Robert H..(2018).Highly Active Platinum Catalysts for Nitrile and Cyanohydrin Hydration: Catalyst Design and Ligand Screening via High-Throughput Techniques.Journal of the American Chemical Society,140(50),17782-17789.

Xing, Xiangyou,et al."Highly Active Platinum Catalysts for Nitrile and Cyanohydrin Hydration: Catalyst Design and Ligand Screening via High-Throughput Techniques".Journal of the American Chemical Society 140.50(2018):17782-17789.