A self-hydrosilylation of phosphanylhydrosilylalkynes promoted by B(C6F5)(3)? An experimental and mechanistic study

作者：Huang, Yanting; Wang, Xiaoping; Li, Yan^*; Yang, Ming-Chung; Su, Ming-Der^*; Zhu, Hongping^*

来源：Chemical Communications, 2019, 55(10): 1494-1497.

DOI：10.1039/c8cc09022j

• H-B BRIDGES
• LEWIS
• HYDROSILATION
• 1,1-ORGANOBORATION
• ACTIVATION
• ELEMENTS
• ALKYNES

Phosphanylhydrosilylalkynes Me2HSiC?CPAr2 (Ar = Ph, 1a; 4-MeC6H4, 1b) were synthesized, which reacted with B(C6F5)(3) to produce alkenes [(E)-(C6F5)(3)BCH?C(PAr2)SiMe2](2) (2a and 2b) and (Z)-(C6F5)(2)BCH?C(PAr2)SiMe2(C6F5) (3a and 3b). The formation of 2a (or 2b) involved a Wrackmeyer's SiHMe2 migration followed by Si-H addition across the C?C bond, whereas, that of 3a (or 3b) involved a similar mechanism with a further C6F5 migration. The B(C6F5)(3)-promoted reaction of the Si-centered geminal H and C?C groups is thus realized, which may be considered as a self-hydrosilylation. Mechanistic studies by both variable temperature NMR spectroscopy and DFT calculations were accomplished.

• 出版日期2019-2-4
• 单位杭州师范大学; 厦门大学