TY - JOUR

T1 - Identification of a potent palladium-aryldiphosphine catalytic system for high-performance carbonylation of alkenes

AU - Zhao, Kang

AU - Wang, Hongli

AU - Li, Teng

AU - Liu, Shujuan

AU - Benassi, Enrico

AU - Li, Xiao

AU - Yao, Yao

AU - Wang, Xiaojun

AU - Cui, Xinjiang

AU - Shi, Feng

N1 - This study was supported by National Natural Science Foundation of China (U22A20393, 21925207 and 22102195), the Youth Innovation Promotion Association of CAS (2019409), the ‘Light of West China’ Program, Key Research Program of Frontier Sciences of CAS (QYZDJSSW-SLH051), the Co-operation Foundation of Dalian National Laboratory for Clean Energy of CAS (DNL201901), Key Program of the Lanzhou Institute of Chemical Physics, CAS (No. KJZLZD-2) and the Major Project of Gansu Province, China (21ZD4WA021). © 2024. The Author(s).

PY - 2024/12

Y1 - 2024/12

N2 - The development of stable and efficient ligands is of vital significance to enhance the catalytic performance of carbonylation reactions of alkenes. Herein, an aryldiphosphine ligand (L11) bearing the [Ph2P(ortho-C6H4)]2CH2 skeleton is reported for palladium-catalyzed regioselective carbonylation of alkenes. Compared with the industrially successful Pd/1,2-bis(di-tert-butylphosphinomethyl)benzene catalyst, catalytic efficiency catalyzed by Pd/L11 on methoxycarbonylation of ethylene is obtained, exhibiting better catalytic performance (TON: >2,390,000; TOF: 100,000 h-1; selectivity: >99%) and stronger oxygen-resistance stability. Moreover, a substrate compatibility (122 examples) including chiral and bioactive alkenes or alcohols is achieved with up to 99% yield and 99% regioselectivity. Experimental and computational investigations show that the appropriate bite angle of aryldiphosphine ligand and the favorable interaction of 1,4-dioxane with Pd/L11 synergistically contribute to high activity and selectivity while the electron deficient phosphines originated from electron delocalization endow L11 with excellent oxygen-resistance stability.

AB - The development of stable and efficient ligands is of vital significance to enhance the catalytic performance of carbonylation reactions of alkenes. Herein, an aryldiphosphine ligand (L11) bearing the [Ph2P(ortho-C6H4)]2CH2 skeleton is reported for palladium-catalyzed regioselective carbonylation of alkenes. Compared with the industrially successful Pd/1,2-bis(di-tert-butylphosphinomethyl)benzene catalyst, catalytic efficiency catalyzed by Pd/L11 on methoxycarbonylation of ethylene is obtained, exhibiting better catalytic performance (TON: >2,390,000; TOF: 100,000 h-1; selectivity: >99%) and stronger oxygen-resistance stability. Moreover, a substrate compatibility (122 examples) including chiral and bioactive alkenes or alcohols is achieved with up to 99% yield and 99% regioselectivity. Experimental and computational investigations show that the appropriate bite angle of aryldiphosphine ligand and the favorable interaction of 1,4-dioxane with Pd/L11 synergistically contribute to high activity and selectivity while the electron deficient phosphines originated from electron delocalization endow L11 with excellent oxygen-resistance stability.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85186931560&origin=inward&txGid=ea0d1caf4a0523941aec6f859d6699ed

U2 - 10.1038/s41467-024-46286-9

DO - 10.1038/s41467-024-46286-9

M3 - Article

C2 - 38443382

VL - 15

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

IS - 1

M1 - 2016

ER -