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

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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.

Original languageEnglish
Pages (from-to)1580-1590
Number of pages11
JournalZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Volume64
Issue number11-12
DOIs
Publication statusPublished - Dec 2009

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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