Organic Chemistry Portal

Abstracts

Search:

Synthesis of Structurally Diverse Allylsilanes via Copper-Catalyzed Regiodivergent Hydrosilylation of 1,3-Dienes

Zi-Lu Wang, Ying Wang, Jian-Lin Xu, Meng Zhao, Kai-Yang Dai, Cui-Cui Shan and Yun-He Xu*

*Department of Chemistry and Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, P.R. China, Email: xyh0709ustc.edu.cn

Z.-L. Wang, Y. Wang, J.-L. Xu, M. Zhao, K.-Y. Dai, C.-C. Shan, Y.-H. Xu, Org. Lett., 2021, 23, 4736-4742.

DOI: 10.1021/acs.orglett.1c01455



see article for more reactions

Abstract

Copper-catalyzed regiodivergent hydrosilylation reactions of substituted 1,3-dienes with hydrosilanes provide 1,2- and 1,4-hydrosilylated products depending on the catalytic systems. A 1,4-hydrosilylation reaction of 2-aryl-substituted 1,3-dienes with diphenylsilane was also successfully realized. These methods provide convenient and efficient approaches to structurally diverse allylsilanes.


see article for more examples



Regioselective 1,2-hydrosilylation of 1-substituted 1,3-dienes

In an oven dried 10-mL Schlenk tube charged with a stir bar was added Cu(etacac)2 (0.01 mmol, 3.2 mg), dppp (0.01 mmol, 4.1 mg), 0.3 mL dry THF and Ph2SiH2 (0.4 mmol, 73.7 mg) in sequence. The system was stirred for 30 min at rt, then, the corresponding 1,3-diene (0.2 mmol) was added and the inner wall of the Schlenk tube was washed with 0.2 mL dry THF. The reaction mixture was stirred for 20 h at 60 C in an oil bath. After completion, ethyl acetate was added and the precipitate was removed by filtration. The resultant solution was concentrated and the crude product was purified by column chromatography.

Regioselective 1,4-hydrosilylation of 2-substituted 1,3-dienes

In an oven dried 10-mL Schlenk tube charged with a stir bar was added Cu(etacac)2 (0.02 mmol, 6.4 mg), dppp (0.02 mmol, 8.2 mg), 0.3 mL Et2O and Ph2SiH2 (0.4 mmol, 73.7 mg) in sequence. The system was stirred for 30 min at rt, then, the corresponding 1,3-diene (0.2 mmol) was added and the inner wall of the Schlenk tube was washed with 0.2 mL Et2O. The reaction mixture was stirred for 20 h at 60 C in an oil bath. After completion, ethyl acetate was added and the precipitate was removed by filtration. The resultant solution was concentrated and the crude products was purified by column chromatography.


Copper-Catalyzed Markovnikov Selective 3,4-Hydrosilylation of 2-Substituted 1,3-Dienes

Y. Wang, Z.-L. Wang, W.-W. Ma, Y.-H. Xu, Org. Lett., 2022, 24, 4081-4086.


Key Words

allylsilanes


ID: J54-Y2021