Nickel-Catalyzed Mono- and Dihydrosilylation of Aliphatic Alkynes in Aqueous and Aerobic Conditions

• Published in: ACS catalysis 2024-04, Vol.14 (7), p.5077-5087
• Main Authors: Lee, Chanmi, Jeon, Ji Hwan, Lee, Soochan, Choe, Wonyoung, Kwak, Jaesung, Seo, Sangwon, Hong, Sung You, Jung, Byunghyuck
• Format: Article
• Language: English
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.4c00109

1,1-Disilanes are synthetically versatile building blocks, owing to their low toxicity, high stability, and unique structures. However, the practical synthesis of 1,1-disilanes is still a challenge. Despite the available Fe-, Co-, La-, and B-catalyzed protocols, the use of highly reactive reductants, such as EtMgBr, NaBHEt3, or KHMDS, inevitably requires air- and moisture-free conditions. Herein, we report the homogeneous Ni-catalyzed mono- and dihydrosilylation of aliphatic terminal alkynes under either air and water conditions or neat conditions, affording β-(E)-vinylsilanes and 1,1-disilanes in high yields with complete regioselectivity and stereoselectivity. Importantly, our method is gram-scalable and the sole example of Ni-catalyzed dihydrosilylation of alkynes. We demonstrated the introduction of different silyl groups through the stepwise addition of each silane source in a reaction vessel. Furthermore, the reaction intermediates were characterized with spectroscopic/spectrometric tools, and density functional theory calculations were performed to understand the reaction mechanism and the origins of the regioselectivity for β-(E)-vinylsilanes and 1,1-disilanes.