Platinum-catalyzed double silylations of alkynes with bis(dichlorosilyl)methanes

Bis(dichlorosilyl)methanes 1 undergo the two kind reactions of a double hydrosilylation and a dehydrogenative double silylation with alkynes 2 such as acetylene and activated phenyl-substituted acetylenes in the presence of Speier’s catalyst to give 1,1,3,3-tetrachloro-1,3-disilacyclopentanes 3 and 1,1,3,3-tetrachloro-1,3-disilacyclopent-4-enes 4 as cyclic products, respectively, depending upon the molecular structures of both bis(dichlorosilyl)methanes (1) and alkynes (2). Simple bis(dichlorosilyl)methane (1a) reacted with alkynes [R1–CC–R2: R1 = H, R2 = H (2a), Ph (2b); R1 = R2 = Ph (2c)] at 80 °C to afford 1,1,3,3-tetrachloro-1,3-disilacyclopentanes 3 as the double hydrosilylation products in fair to good yields (33–84%). Among these reactions, the reaction with 2c gave a trans-4,5-diphenyl-1,1,3,3-tetrachloro-1,3-disilacyclopentane 3ac in the highest yield (84%). When a variety of bis(dichlorosilyl)(silyl)methanes [(MenCl3 − nSi)CH(SiHCl2)2: n = 0 (1b), 1 (1c), 2 (1d), 3 (1e)] were applied in the reaction with alkyne (2c) under the same reaction conditions. The double hydrosilylation products, 2-silyl-1,1,3,3-tetrachloro-1,3-disilacyclopentanes (3), were obtained in fair to excellent yields (38–98%). The yields of compound 3 deceased as follows: n = 1 > 2 > 3 > 0. The reaction of alkynes (2a–c) with 1c under the same conditions gave one of two type products of 1,1,3,3-tetrachloro-1,3-disilacyclopentanes 3 and 1,1,3,3-tetrachloro-1,3-disilacyclopent-4-enes (4): simple alkyne 2a and terminal 2b gave the latter products 4ca and 4cb in 91% and 57% yields, respectively, while internal alkyne 2c afforded the former cyclic products 3cc with trans form between two phenyl groups at the 3- and 4-carbon atoms in 98% yield, respectively. Among platinum compounds such as Speier’s catalyst, PtCl2(PEt3)2, Pt(PPh3)2(C2H4), Pt(PPh3)4, Pt[ViMeSiO]4, and Pt/C, Speier’s catalyst was the best catalyst for such silylation reactions.

Graphical abstractReaction of alkynes such as ethene (2a), phenylethene (2b); 1,2-diphenylethene (2c) with bis(dichlorosilyl)methanes RCH(SiHCl2)2: R = H (1a), SiMenCl3 − n: n = 0 (1b), 1 (1c), 2 (1d), 3 (1e) in the presence of Speier’s catalyst gave one of two type products of 1,3-disilacyclopentanes 3 and 1,3-disilacyclopent-4-enes 4. Reaction of 1a with 2a–c at 80 °C gave compounds 3 in 33–84% yields. The reaction with 2c gave 3ac in the highest yield (84%). Reaction of 1b–e with 2c under the same conditions gave compounds 3 in 38–98% yields. The yields deceased in following order: n = 1 > 2 > 3 > 0. Reactions of 1c with simple 2a and terminal 2b under the same conditions gave 4ca and 4cb in 91% and 57% yields, respectively, while internal alkyne 2c afforded 3cc in 98% yield.Figure optionsDownload full-size imageDownload as PowerPoint slide