Transition-Metal Reactions of Benzodisilacyclobutenes

本文报道了铂催化异丙取代苯二二环丁烯的反应。3,4 -苯并- 1,1,2,2 -四（异丙基）- 1,2 -二-无环丁-3-烯(1)与苯乙炔和1-己炔在（eta^2-乙烯）双（三苯基膦）铂(O)的催化量下，在200℃下反应24h，得到两种类型的1：2-苯基和2-丁基分别取代5,6 -苯- 1,1,4,4 -四（异丙基）- 1,4 -二硅环己- 2,5 -二烯和2-苄基-和2-戊基-分别取代4,5 -苯- 1,1,3,3 -四（异丙基）- 1,3 -二硅环- 4烯。与甲酰基和二甲基苯基硅基乙炔，1得到2-（甲酰基）亚甲基-和2-（二甲基苯基硅基）-亚甲基4,5 -苯并- 1,1,3,3 -四（异戊基）- 1,3 -二硅环-4-烯。i与三甲基硅基乙炔的类似反应由乙炔的sp-杂化C-H键活化生成加成物，并生成苯二苯环戊烯衍生物。1 w . More与去苯基乙炔反应得到2,3 -二苯基- 5,6 -苯并二硅环己- 2,5 -二烯衍生物，与亚苯基乙炔和2-己炔反应得到2-苄基-和2-丁基- 5,6 -苯并- 1,4 -顺硅环己-5-烯衍生物，以及苯并二硅环己- 2,5 -二烯衍生物。1与甲基（三甲基硅基）乙炔的类似处理产生5,6 -苯并-2-（三甲基硅基）亚二硅环己烯衍生物。本文还报道了苯并双环丁烯的合成及其在铂和钯催化下的反应。以1,2,4,5 -四氨基苯和镁为原料，在二乙基氟硅烷的存在下，在四氢呋喃中合成了苯并[1,2,4,5]二（1,1,2,2 -四乙基- 1,2 -二酰基-3-丁烯）(2)。1与二苯基乙炔在（eta^2-乙烯）双（三苯基膦）铂(O)的催化量下，在松紧苯中反应得到1:1 -2加合物苯并[1,2,4,5]双（1,1,4,4 -四乙基- 2,3 -二苯基- 1,4 -二酰基- 2,5 -二烯），收率为91%。在回流苯中，类似的铂(O)催化1与3-己炔和乙炔的反应产生了各自的1:1 - 2加合物，苯并[1,2,4,5]双（二环己二烯）衍生物，收率很高。在催化量的四（三苯基膦）钯(O)存在下，苯并双（二苯环丁烯）1也与二苯基乙炔、3-己炔和乙炔反应，得到相应的1:1加合物，产率很高。少

In this paper we report the platinum-catalyzed reactions of isopmpy-substituted benzodisilacyclobutene. The reactions of 3, 4-benzo-1, 1, 2, 2-tetra(isopropy1)-l, 2-disi1acyclobut-3-ene (1) with phenylacetylene and 1-hexyne in the presence of a catalytic amount of (eta^2-ethylene)bis(tripheny1phosphine)platinum(O) at 200ﾟC for 24h gave two types of 1 : 1 ackiucts, 2-phenyl- and 2-butyl-substituted 5, 6-benzo-1 , 1 , 4, 4-tetra(isopropyl)- 1 , 4-disilacyclohexa-2, 5-diene and 2-benzylidene- and 2-pentylidene-substituted 4, 5-benzo- 1, 1 , 3, 3-tetra(isopropyl)-1, 3-disilacyclopent-4ene, respectively. With mesityl- and dimethylphenylsilylacetylene, 1 afforded 2-(mesityl)methylene- and 2-(dimethylphenylsilyl)- methylene4, 5-benzo-1, 1, 3 , 3-tetra(isopmpyl)-1 , 3disilacyclopent-4-ene. Similar reaction of i with trimethylsilyl-acetylene produced an adduict ansing from sp-hybridized C-H bond activation of the acetylene, together with a benzodisilacyclopentene derivative. The reaction of 1 w … More ith dephenylacetylene yielded a 2, 3-diphenyl-5, 6-benzodisilacyclohexa-2, 5-diene derivative, while with methyiphenylacetylene and 2-hexyne, 1 gave 2-benzylidene- and 2-butylidene-5, 6-benzo-1 , 4-cisilacyclohex-5-ene, along with the benzodisilacyclohexa-2, 5-diene deriivatives. Similar treatment of 1 with methyl(trimethylsilyl)acetylene produced a 5, 6-benzo-2-(trimethylsilyl)methylenedisilacyclohexene derivative.We also report the synthesis and platinum- and palladium-catalyzed reactions of benzobis(disilacyclobutene). Benzo[1 , 2 : 4, 5]bis(1, 1 , 2, 2-tetraethyl-1 , 2-disilacyclobut-3-ene) (2) was synthesized by the reaction of1, 2, 4, 5-tetrabmmobenzene with magnesium in the presence of diethyifluorosilane in THF.The reaction of 1 with diphenylacetylene in the presence of a catalytic amount of (eta^2-ethylene)bis(triphenylphosphine)platinum(O) in relluxing benzene gave a 1 : 2-adduct, benzo[1 , 2 : 4, 5]bis(1, 1, 4, 4-tetraethyl -2, 3-diphenyl- 1 , 4-disilacyclohexa-2, 5-diene) in 91% yield. Similar platinum(O)-catalyzed reaction of 1 with 3-hexyne and acetylene in refluxing benzene afforded the respective 1 : 2-adducts, benzo[1 , 2 : 4, 5]bis(disilacyclohexadiene) derivatives in excellent yields. Benzobis(disilacyclobutene) 1 also reacted with diphenylacetylene, 3-hexyne, and acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(O) to give the corresponding 1 : 2 adducts in excellent yields. Less