Stereochemistry of Disilanylene-containing Cyclic Compounds - Synthesis and Palladium-catalyzed Reactions of cis- and trans-3,4- Benzo-1,2-diisopropyl-1,2-dimethyl-1,2-disilacyclobut-3-ene

Akinobu Naka, Jun Sakata, Junnai Ikadai, Hiroyuki Kawasaki, Joji Ohshita, Eigo Miyazaki, Atsutaka Kunai, Mitsuo Ishikawa, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

4 引用 (Scopus)

抄録

The synthesis and palladium-catalyzed reactions of cis- and trans-3,4-benzo-1,2-diisopropyl- 1.2- dimethyl-1,2-disilacyclobut-3-ene (1a and 1b) are reported. Their reactions with diphenyl- acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) proceeded with high stereospecificity to give cis- and trans-5,6-benzo-1,4-diisopropyl-1,4-dimethyl- 2.3- diphenyl-1,4-disilacyclohexa-2,5-diene, 2a and 2b, in 95% and 93% yield, respectively. Similar palladium-catalyzed reactions of 1a and 1b with monosubstituted acetylenes, such as 1-hexyne, tert-butylacetylene, phenylacetylene, and trimethylsilylacetylene, also proceeded stereospecifically to afford the respective cis- and trans-5,6-benzo-1,4-disilacyclohexa-2,5-dienes, 3a -6a and 3b - 6b, in excellent yields and as the sole products. The palladium-catalyzed reaction of 1a with styrene gave a mixture consisting of two stereoisomers, cis-2- and trans-2-phenyl-substituted 5,6- benzo-(r-1),cis-4-diisopropyl-1,4-disilacyclohex-5-ene 7a and 8a in a ratio of 5:3 in 72% combined yield, while the reaction of styrene with 1b afforded two stereoisomers, 7b and 8b, in a ratio of 2:1 in 80% combined yield. With 1-hexene, 1a gave two stereoisomers, 5,6-benzo-cis-2-(n- butyl)-(r-1),cis-4-diisopropyl- and 5,6-benzo-trans-2-(n-butyl)-(r-1),cis-4-diisopropyl-1,4-dimethyl-1.4- disilacyclohex-5-ene, 9a and 10a, in a ratio of 1: 1 in 70 % combined yield. A similar reaction of 1b with 1-hexene produced 5,6-benzo-cis-2-(n-butyl)-(r-1),trans-4-diisopropyl-1,4-dimethyl-1,4- disilacyclohex-5-ene in 81 % yield and as a single isomer.

元の言語英語
ページ(範囲)1580-1590
ページ数11
ジャーナルZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
64
発行部数11-12
DOI
出版物ステータス出版済み - 1 1 2009

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Stereochemistry
Palladium
Stereoisomerism
Styrene
Acetylene
Alkynes
Isomers
diphenyl
1-hexene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

これを引用

Stereochemistry of Disilanylene-containing Cyclic Compounds - Synthesis and Palladium-catalyzed Reactions of cis- and trans-3,4- Benzo-1,2-diisopropyl-1,2-dimethyl-1,2-disilacyclobut-3-ene. / Naka, Akinobu; Sakata, Jun; Ikadai, Junnai; Kawasaki, Hiroyuki; Ohshita, Joji; Miyazaki, Eigo; Kunai, Atsutaka; Ishikawa, Mitsuo; Yoshizawa, Kazunari.

:: Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 巻 64, 番号 11-12, 01.01.2009, p. 1580-1590.

研究成果: ジャーナルへの寄稿記事

Naka, Akinobu ; Sakata, Jun ; Ikadai, Junnai ; Kawasaki, Hiroyuki ; Ohshita, Joji ; Miyazaki, Eigo ; Kunai, Atsutaka ; Ishikawa, Mitsuo ; Yoshizawa, Kazunari. / Stereochemistry of Disilanylene-containing Cyclic Compounds - Synthesis and Palladium-catalyzed Reactions of cis- and trans-3,4- Benzo-1,2-diisopropyl-1,2-dimethyl-1,2-disilacyclobut-3-ene. :: Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences. 2009 ; 巻 64, 番号 11-12. pp. 1580-1590.
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title = "Stereochemistry of Disilanylene-containing Cyclic Compounds - Synthesis and Palladium-catalyzed Reactions of cis- and trans-3,4- Benzo-1,2-diisopropyl-1,2-dimethyl-1,2-disilacyclobut-3-ene",
abstract = "The synthesis and palladium-catalyzed reactions of cis- and trans-3,4-benzo-1,2-diisopropyl- 1.2- dimethyl-1,2-disilacyclobut-3-ene (1a and 1b) are reported. Their reactions with diphenyl- acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) proceeded with high stereospecificity to give cis- and trans-5,6-benzo-1,4-diisopropyl-1,4-dimethyl- 2.3- diphenyl-1,4-disilacyclohexa-2,5-diene, 2a and 2b, in 95{\%} and 93{\%} yield, respectively. Similar palladium-catalyzed reactions of 1a and 1b with monosubstituted acetylenes, such as 1-hexyne, tert-butylacetylene, phenylacetylene, and trimethylsilylacetylene, also proceeded stereospecifically to afford the respective cis- and trans-5,6-benzo-1,4-disilacyclohexa-2,5-dienes, 3a -6a and 3b - 6b, in excellent yields and as the sole products. The palladium-catalyzed reaction of 1a with styrene gave a mixture consisting of two stereoisomers, cis-2- and trans-2-phenyl-substituted 5,6- benzo-(r-1),cis-4-diisopropyl-1,4-disilacyclohex-5-ene 7a and 8a in a ratio of 5:3 in 72{\%} combined yield, while the reaction of styrene with 1b afforded two stereoisomers, 7b and 8b, in a ratio of 2:1 in 80{\%} combined yield. With 1-hexene, 1a gave two stereoisomers, 5,6-benzo-cis-2-(n- butyl)-(r-1),cis-4-diisopropyl- and 5,6-benzo-trans-2-(n-butyl)-(r-1),cis-4-diisopropyl-1,4-dimethyl-1.4- disilacyclohex-5-ene, 9a and 10a, in a ratio of 1: 1 in 70 {\%} combined yield. A similar reaction of 1b with 1-hexene produced 5,6-benzo-cis-2-(n-butyl)-(r-1),trans-4-diisopropyl-1,4-dimethyl-1,4- disilacyclohex-5-ene in 81 {\%} yield and as a single isomer.",
author = "Akinobu Naka and Jun Sakata and Junnai Ikadai and Hiroyuki Kawasaki and Joji Ohshita and Eigo Miyazaki and Atsutaka Kunai and Mitsuo Ishikawa and Kazunari Yoshizawa",
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doi = "10.1515/znb-2009-11-1243",
language = "English",
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T1 - Stereochemistry of Disilanylene-containing Cyclic Compounds - Synthesis and Palladium-catalyzed Reactions of cis- and trans-3,4- Benzo-1,2-diisopropyl-1,2-dimethyl-1,2-disilacyclobut-3-ene

AU - Naka, Akinobu

AU - Sakata, Jun

AU - Ikadai, Junnai

AU - Kawasaki, Hiroyuki

AU - Ohshita, Joji

AU - Miyazaki, Eigo

AU - Kunai, Atsutaka

AU - Ishikawa, Mitsuo

AU - Yoshizawa, Kazunari

PY - 2009/1/1

Y1 - 2009/1/1

N2 - The synthesis and palladium-catalyzed reactions of cis- and trans-3,4-benzo-1,2-diisopropyl- 1.2- dimethyl-1,2-disilacyclobut-3-ene (1a and 1b) are reported. Their reactions with diphenyl- acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) proceeded with high stereospecificity to give cis- and trans-5,6-benzo-1,4-diisopropyl-1,4-dimethyl- 2.3- diphenyl-1,4-disilacyclohexa-2,5-diene, 2a and 2b, in 95% and 93% yield, respectively. Similar palladium-catalyzed reactions of 1a and 1b with monosubstituted acetylenes, such as 1-hexyne, tert-butylacetylene, phenylacetylene, and trimethylsilylacetylene, also proceeded stereospecifically to afford the respective cis- and trans-5,6-benzo-1,4-disilacyclohexa-2,5-dienes, 3a -6a and 3b - 6b, in excellent yields and as the sole products. The palladium-catalyzed reaction of 1a with styrene gave a mixture consisting of two stereoisomers, cis-2- and trans-2-phenyl-substituted 5,6- benzo-(r-1),cis-4-diisopropyl-1,4-disilacyclohex-5-ene 7a and 8a in a ratio of 5:3 in 72% combined yield, while the reaction of styrene with 1b afforded two stereoisomers, 7b and 8b, in a ratio of 2:1 in 80% combined yield. With 1-hexene, 1a gave two stereoisomers, 5,6-benzo-cis-2-(n- butyl)-(r-1),cis-4-diisopropyl- and 5,6-benzo-trans-2-(n-butyl)-(r-1),cis-4-diisopropyl-1,4-dimethyl-1.4- disilacyclohex-5-ene, 9a and 10a, in a ratio of 1: 1 in 70 % combined yield. A similar reaction of 1b with 1-hexene produced 5,6-benzo-cis-2-(n-butyl)-(r-1),trans-4-diisopropyl-1,4-dimethyl-1,4- disilacyclohex-5-ene in 81 % yield and as a single isomer.

AB - The synthesis and palladium-catalyzed reactions of cis- and trans-3,4-benzo-1,2-diisopropyl- 1.2- dimethyl-1,2-disilacyclobut-3-ene (1a and 1b) are reported. Their reactions with diphenyl- acetylene in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium(0) proceeded with high stereospecificity to give cis- and trans-5,6-benzo-1,4-diisopropyl-1,4-dimethyl- 2.3- diphenyl-1,4-disilacyclohexa-2,5-diene, 2a and 2b, in 95% and 93% yield, respectively. Similar palladium-catalyzed reactions of 1a and 1b with monosubstituted acetylenes, such as 1-hexyne, tert-butylacetylene, phenylacetylene, and trimethylsilylacetylene, also proceeded stereospecifically to afford the respective cis- and trans-5,6-benzo-1,4-disilacyclohexa-2,5-dienes, 3a -6a and 3b - 6b, in excellent yields and as the sole products. The palladium-catalyzed reaction of 1a with styrene gave a mixture consisting of two stereoisomers, cis-2- and trans-2-phenyl-substituted 5,6- benzo-(r-1),cis-4-diisopropyl-1,4-disilacyclohex-5-ene 7a and 8a in a ratio of 5:3 in 72% combined yield, while the reaction of styrene with 1b afforded two stereoisomers, 7b and 8b, in a ratio of 2:1 in 80% combined yield. With 1-hexene, 1a gave two stereoisomers, 5,6-benzo-cis-2-(n- butyl)-(r-1),cis-4-diisopropyl- and 5,6-benzo-trans-2-(n-butyl)-(r-1),cis-4-diisopropyl-1,4-dimethyl-1.4- disilacyclohex-5-ene, 9a and 10a, in a ratio of 1: 1 in 70 % combined yield. A similar reaction of 1b with 1-hexene produced 5,6-benzo-cis-2-(n-butyl)-(r-1),trans-4-diisopropyl-1,4-dimethyl-1,4- disilacyclohex-5-ene in 81 % yield and as a single isomer.

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