Synthesis and Polyaddition Reaction of Optically Active Methylphenylpropargylsilane

Chromatographic separation of asymmetric organosilicon compounds on cellulose and amylose stationary phases. The stereochemistry of functional transformation reactions

“…Alkylation by use of a Grignard reagent is also reported to proceed with inversion of the absolute configuration at the silicon chiral center at low temperature. Si-(S)-2(+)f and 2(+)h obtained with 100% optical purity from Si-(R)-2(+)a were 78 and 73% optically pure when evaluated by 1H NMR of the isopropyl signal of the menthoxy group [9,10]. In this reaction bromination is considered to result in ca 75% inversion.…”

“…The absolute configuration is considered to be rich in the (R) configuration, because it is reported that brominative cleavage of the Si Np bond is a process with ca 80 85% inversion of stereochemistry of the silicon atom, and it has been shown that the reduction is a process with retention of the absolute configuration at the silicon atom [9,19,20]. We have suggested that stereochemistry is retained during reduction and hydrosilylation [8,10] and have reported that the optically active chlorosilane is susceptible to racemization when heated in a polar solvent [16]. The reaction to give ld was slow and required a long reaction time, with heating.…”

“…Isotactic poly[(methylphenylsilylene)(trimethylene)] [8,9], isotactic and optically active poly[(methylphenylsilylene) (2-propenylene)] [10], and poly[oxy(dimethylsilylene)ethylene { (1 -naphthyl)phenylsilylene}] [11,12], respectively, were obtained from these monomers. Optically active poly[(3S,5S)-1,1,3,5-tetramethyl-3,5-diphenyl-l,3,5-trisiloxane] [13] has also been reported.…”

Functionality and stereochemical design of silicon-containing polymers

“…Recently, we found that the introduction of a methoxy group at the 4-position of the naphthyl group improved the d. e. of 2 as high as 91% 64) . Optically active propargylsilane is synthesized similarly (Scheme 5) 65) . The reduction of (S)-methylphenyl- Another practical method to obtain stereoregular polycarbosilane is the ring-opening polymerization of optically active silacyclobutanes.…”

Formation of Poly(silsesquioxane) Gel Containing Optically Active 1,3-Dimethyl-1,3-diphenyldisiloxane as a Connecting Unit

“…1 However, chiral separation materials with chirality induced by asymmetric silicon atoms in the main chain have not been reported yet. We have prepared several optically active polymers having asymmetric silicon atoms in the main chain, [2][3][4][5] and are moving toward finding possible application of these polymers as a new class of chiral separation materials based on the property derived from the asymmetry of the silicon atom itself in the polymer backbone.…”