Stereochemistry of disilanylene-containing cyclic compounds. Synthesis andreactions of cis- and trans-1,2-dimethyl-1,2-diphenyl-1,2-disilacyclopentanes

Citation
A. Naka et al., Stereochemistry of disilanylene-containing cyclic compounds. Synthesis andreactions of cis- and trans-1,2-dimethyl-1,2-diphenyl-1,2-disilacyclopentanes, ORGANOMETAL, 20(6), 2001, pp. 1204-1209
Citations number
13
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
0276-7333 → ACNP
Volume
20
Issue
6
Year of publication
2001
Pages
1204 - 1209
Database
ISI
SICI code
0276-7333(20010319)20:6<1204:SODCCS>2.0.ZU;2-6
Abstract
The Wurtz type coupling of a mixture of meso- and dl-1,3-bis(chloromethylph enylsilyl)propanes with sodium metal afforded a mixture of cis- and trans-d isilacyclopentanes (1a and 1b) in a ratio of 1:1. Pure la and Ib obtained b y fractional distillation reacted with molecular oxygen in the presence of AlBN stereospecifically to give the respective cis- and trans-cyclic siloxa nes (2a and 2b), with retention of configuration. The reactions of la and I b with MCPBA produced cleanly 2a and 2b in high yields, respectively. The p alladium-catalyzed reactions of la and Ib with phenylacetylene gave stereos pecifically cis- and trans-1,4-dimethyl-1,2,4-triphenyl-1,4-disilacyclohept -2-enes (3a and 3b), in high yields. Similar treatment of la and Ib with di phenylacetylene also proceeded with high stereospecificity to give cis- and trans-1,4-dimethyl-1,2,3,4-tetraphenyl-1 (4a and 4b), respectively. The re sults of an X-ray crystallographic study for products 4a and 4b are describ ed.