Silaheterocycles. 32.¹ Facile Synthesis of 3-Alkoxy-1-silacyclobutanes from the Trichlorovinylsilane/t-BuLi Reagent and Vinyl Ethers

Abstract

Equimolar mixtures of trichlorovinylsilane and t-BuLi (1) were reacted with different vinyl ethers, CH 2 dCH-OR (R ) Et, n-Pr, n-Bu, i-Bu, t-Bu), to yield the silacyclobutanes 2-6. NMR spectroscopic investigations showed the addition of the formal silene unit Cl 2 Sid CHCH 2 t-Bu to the vinyl group of the vinyl ethers to be stereo-and regiospecific, forming products of E-configuration. In contrast, in the presence of bisvinyl [CH 2 dCH-O-(CH 2 ) n -O-CHdCH 2 (n ) 2, 4, 6)] or cyclic vinyl ethers, such as 2,3-dihydrofuran and 3,4-dihydro-2H-pyran, the formation of silacylobutanes was suppressed and the formation of addition and SiCl/CHLi coupling products, such as Cl 2 (R)SiCH 2 CH 2 t-Bu (RdCl, 7; t-Bu, 8) and the tetrachloro-1,3-disilacyclobutane, (Cl 2 SiCHCH 2 t-Bu) 2 (10), was favored. Compounds 8 and 10 were characterized by single-crystal X-ray diffraction studies.

Silacyclobutane‐functionalized cyclosiloxanes as photoactive precursors for high thermal stability, low dielectric constant and low dielectric loss polymers

“…26,27 These low dielectric materials have been shown to be suitable for high temperature applications. 28 The cyclic moieties in these polymers can also serve as cross-linking sites, meaning that, if SCB groups can be incorporated into cyclosiloxanes, the resulting materials could undergo ring-opening polymerization in response to heat or irradiation, to generate hypercross-linked siloxane-carbosilane networks.…”

“…On the basis of the above, in addition to results from our earlier work regarding the synthesis of silicon-based polymers, [28][29][30][31] the present study explored the efficient, facile synthesis of silacyclobutane-functionalized cyclosiloxanes via simple hydrolysis or alcoholysis reactions using 1,1dichlorosilacyclobutane (DCSCB). The polymerization of these compounds was assessed.…”

Silylene Transfer to Allylic Sulfides: Formation of Substituted Silacyclobutanes

“…2 These silanes are synthesized conventionally by intramolecular Wurtz-type coupling 3-6 or [2+2] cycloaddition reactions, 7,8 making additional synthetic routes desirable. Unlike three-membered ring silanes, silacyclobutanes are often air stable, which facilitates their handling and manipulation.…”

“…Silacyclobutanes are unique strained-ring compounds that have been used in a variety of chemical applications, including ring-opening polymerization . These silanes are synthesized conventionally by intramolecular Wurtz-type coupling − or [2+2] cycloaddition reactions, , making additional synthetic routes desirable. Unlike three-membered-ring silanes, silacyclobutanes are often air stable, which facilitates their handling and manipulation .…”