Transition-Metal Reactions of small-ring silicon compounds

小环硅化合物的过渡金属反应

• 批准号: 12650858
• 负责人: ISHIKAWA Mitsuo
• 金额: $ 2.37万
• 依托单位: Kawasaki University of Sciense and the Arts
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650858/
• 关键词: Silicon; Transition-metal; Catalyzed Reaction; Cyclobutenc; Cyclopentane; Stereochemistry; 触媒反応

In this paper we report the transition-metal reactions of small-ring compounds containing silicon-silicon bond. The palladium-catalyzed reactions of pure cis-and trans-3, 4-benzo-1, 2-di(tert-butyl)-1, 2-dimethyl1, 2-disilacyclobut-3-ene (1a and 1b) with phenylacetylene and 1-hexyne produced stereospecifically cis-and trans-5, 6-benzo-1, 4-disilacyclohexa-2, 5-dienes.The Wurtz type coupling of a mixture of meso-and dl-1, 3-bis (chloromethylphenylsilyl) propanes with sodium metal afforded a mixture of cis-and trans-disilacyclopentanes (2a and 2b) in a ratio of 1 : 1.The palladium-catalyzed reactions of 2a and 2b with phenylacetylene gave stereospecifically cis-and trans-1, 4-dimethyl-1, 2, 4-triphenyl-1, 4-disilacyclohept-2-enes (3a and 3b), in high yields. Similar treatment of 2a and 2b with diphenylacetylene also proceeded with high stereospecificity to give cis-and trans-1, 4-dimethyl-1, 2, 3, 4-tetraphenyl-1, 4-disilacyclohept-2-enes (4a and 4b), respectively.The platinum-catalyzed … More reactions of 2a with terminal acetylenes such as phenylacetylene and 1-hexyne in a degassed sealed tube at 150℃ for 24h afforded cis-1, 4-dimethyl-1, 2, 4-triphenyl-1, 4-disilacyclohept-2-ene (5a) and cis-2-n-butyl-1, 4-dimethyl-1, 4-diphenyl-1, 4-disilacyclohept-2-ene (6a), respectively, arising from insertion of a triple bond in the acetylenes into a silicon-silicon bond. Similar reactions of 2b with phenylacetylene and 1-hexyne gave trans-1, 4-dimethyl-1, 2, 4-triphenyl-1, 4-disilacyclohept-2-ene (5b) and trans-2-n-butyl-1, 4-dimethyl-1, 4-diphenyl-1, 4-disilacyclohept-2-ene (6b), respectively. The platinum-catalyzed reactions of 2a and 2b with di-substituted acetylenes such as diphenylacetylene, 1-phenyl-1-propyne, and 3-hexyne gave the respective cis-and trans-1, 4-dimetnyl-1, 4-diphenyl-1, 4-disilacyclohept-2-ene derivatives with high stereospecificity. The nickel-catalyzed reactions of 2a and 2b with di-substituted acetylenes also proceeded with high stereospecificity to give the adducts as observed in the platinum-catalyzed reactions.The palladium-catalyzed reaction of 1, 1-dimethyl-2, 2-diphenyl-1, 2-disilacyclopentane (7) with phenylacetylene gave regiospecifically 4, 4-dimethyl-1, 1, 2-triphenyl-1, 4-disilacyclohept-2-ene (8) in 93% yield. Similar treatment of 7 with tert-butylacetylene and 1-hexyne also proceeded with high regiospecificity to give 2-tert-butyl-4, 4-dimethyl-1, 1-diphenyl-1, 4-disilacyclohept-2-ene (9) and 2-n-butyl-4, 4-dimethyl-1, 1-diphenyl-1, 4-disilacyclohept-2-ene (10) in 93% and 90% yields, respectively. The platinum-catalyzed reactions of 7 with phenylacetylene, tert-butylacetylene, and 1-hexyne afforded regiospecifically the same products as those obtained from palladium-catalyzed reactions in high yields. Less

本文报道了含硅-硅键的小环化合物的过渡金属反应。研究了钯催化的顺式和反式-3，4-苯并-1，2-二叔丁基-1，2-二甲基-1，2-二硅杂环丁-3-烯（1a和1b）与苯乙炔和1-己炔反应，立体定向地生成顺式和反式-5，6-苯并-1，4-二硅杂环己-2，5-二烯。3-双（氯甲基苯基甲硅烷基）丙烷与金属钠反应得到顺式和反式二硅杂环戊烷的混合物（2a和2b）以1：1. 2a和2b在钯催化下与苯乙炔反应，立体专一性地得到顺式和反式-1，4-二甲基-1，2，4-三苯基-1，2，4-三嗪，4-二硅杂环庚-2-烯（3a和3b）。用二苯基乙炔对2a和2b进行类似的处理也以高立体特异性进行，分别得到顺式和反式-1，4-二甲基-1，2，3，4-四苯基-1，4-二硅杂环庚-2-烯（4a和4 b）。 ...更多信息 2a与端炔如苯乙炔和1-己炔在脱气密封管中于150℃反应24 h，分别得到顺式-1，4-二甲基-1，2，4-三苯基-1，4-二硅杂环庚-2-烯（5a）和顺式-2-正丁基-1，4-二甲基-1，4-二苯基-1，4-二硅杂环庚-2-烯（6a），由乙炔中的三键插入到硅-硅键中产生。2b与苯乙炔和1-己炔进行类似的反应，分别得到反式-1，4-二甲基-1，2，4-三苯基-1，4-二硅杂环庚-2-烯（5 b）和反式-2-正丁基-1，4-二甲基-1，4-二苯基-1，4-二硅杂环庚-2-烯（6 b）。2a和2b分别与二苯乙炔、1-苯基-1-丙炔和3-己炔等二取代炔类化合物在铂催化下反应，得到了顺式和反式的1，4-二甲基-1，4-二苯基-1，4-二硅杂环庚-2-烯衍生物。2a和2b与二取代乙炔的镍催化反应也具有高度的立体专一性，得到了铂催化反应中观察到的加合物。钯催化的1，1-二甲基-2，2-二苯基-1，2-二硅杂环戊烷（7）与苯乙炔的反应区域专一性地得到了4，4-二甲基-1，1，2-三苯基-1，1，2-二硅杂环戊烷（7）。4-二硅杂环庚-2-烯（8），产率93%。用叔丁基乙炔和1-己炔对7进行类似的处理也具有高的区域特异性，分别以93%和90%的产率得到2-叔丁基-4，4-二甲基-1，1-二苯基-1，4-二硅杂环庚-2-烯（9）和2-正丁基-4，4-二甲基-1，1-二苯基-1，4-二硅杂环庚-2-烯（10）。7与苯乙炔、叔丁基乙炔和1-己炔的铂催化反应以高产率提供了与从钯催化反应获得的产物区域特异性相同的产物。少

项目成果

Mitsuo Ishikawa: "Synthesis and Stereochemistry of cis-and trans-3,4-Benzo-1,2-di(tert-butyl)-1,2-dimethyl-1,2-disilacyclobutene"Organometallics. 20. 1059-1061 (2001)

Mitsuo Ishikawa：“顺式和反式-3,4-苯并-1,2-二（叔丁基）-1,2-二甲基-1,2-二硅杂环丁烯的合成和立体化学”有机金属化合物。

Akinobu Naka: "Regiochemistry of Disilanylene-Containing Cyclic Compounds. Palladium-and Platinum-Catalyzed Reactions of 1, 1-Dimethyl-2, 2-diphenyl-1, 2-disilacyclopentane"Organometallics. 20・8. 1695-1698 (2001)

Akinobu Naka：“含二硅基的环状化合物的区域化学。1, 1-二甲基-2, 2-二苯基-1, 2-二硅杂环戊烷的钯和铂催化反应”有机金属学 20・8。

Seung-Cha: "Stereochemistry of Disilanylene-Containing Cyclic Compounds.Synthesis and Reactions of cis-and trans-1,2-Dimethyl-1,2-diphenyl-1,2-disilacyclohexane"Organometallics. 20. 3718-3723 (2001)

Seung-Cha：“含二硅基环状化合物的立体化学。顺式和反式-1,2-二甲基-1,2-二苯基-1,2-二硅杂环己烷的合成和反应”有机金属化合物。

Seung-Hun, Cha. Kyung, Koo, Lee. Young-Woo, Kwak. Heung-Jin, Choi. Yeon, Sil, Park. Akinobu, Naka. And Mitsuo, Ishikawa: "Stereochemistry of Disilanylene-Containing Cyclic Compounds. Synthesis and Reactions of cis- and trans-1, 2-Dimethy1-1, 2-dipheny1-1,

车胜勋，车.

Akinobu Naka: "Stereochemistry of Disilanylene-Containing Cyclic Compounds. Synthesis and Reactions of cis-and trans-1, 2-Dimethyl-1, 2-diphenyl-1, 2-disilacyclopentanes"Organometallics. 20・6. 1204-1209 (2001)

Akinobu Naka：“含二硅烷基的环状化合物的立体化学。顺式和反式-1, 2-二甲基-1, 2-二苯基-1, 2-二硅杂环戊烷的合成和反应”有机金属学 1204-1209。 ）