Control of stereochemical structures of silicon-containing polymeric systems†

  title={Control of stereochemical structures of silicon-containing polymeric systems†},
  author={Yusuke Kawakami and Yuriko Kakihana and Osamu Ooi and Motoi Oishi and Keigo Suzuki and Satoshi Shinke and Kazuya Uenishi},
  journal={Polymer International},
Various optically active silicon compounds have been synthesized or separated, and used to synthesize silicon-containing polymers with well-controlled stereochemical structures. Hydrosilylation, anionic ring-opening polymerization and cross-coupling reactions have been used to synthesize optically active and/or stereoregular silicon-containing polymers. Copyright © 2009 Society of Chemical Industry 
11 Citations
Enantioselective Construction of Si-Stereogenic Center via Rhodium-Catalyzed Intermolecular Hydrosilylation of Alkene.
A rhodium-catalyzed regio- and enantio-selective intermolecular hydrosilylation of alkene with prochiral dihydrosilane is reported, which features a simple catalytic system, mild reaction conditions and a wide functional group tolerance. Expand
Asymmetric Synthesis of Silicon-Stereogenic Vinylhydrosilanes by Cobalt-Catalyzed Regio- and Enantioselective Alkyne Hydrosilylation with Dihydrosilanes.
An unprecedented cobalt-catalyzed asymmetric hydrosilylation of unsymmetric alkynes with dihydrosilanes that furnishes silicon-stereogenic vinylhydrosILanes with high regio- and enantioselectivity is reported. Expand
Enantioselective Construction of Silicon-Stereogenic Silanes by Scandium-Catalyzed Intermolecular Alkene Hydrosilylation.
The enantioselective hydrosilylation of alkenes with dihydrosilanes by a chiral half-sandwich scandium catalyst constitutes an efficient and general route for the synthesis of a wide range of enantioenriched silicon-stereogenic silanes from easily accessible starting materials. Expand
Asymmetric Synthesis of Silicon-Stereogenic Silanes by Copper-Catalyzed Desymmetrizing Protoboration of Vinylsilanes.
  • Ge Zhang, Yanfei Li, Ying Wang, Qian Zhang, T. Xiong, Qian Zhang
  • Medicine, Chemistry
  • Angewandte Chemie
  • 2020
An unprecedented copper-catalyzed desymmetrizing protoboration of divinyl substituted silanes with bis(pinacolato)diboron (B 2 pin 2) allows facile preparation of an array of enantiomerically enriched boronate-substituted organosilanes bearing contiguous silicon- and carbon-stereocenters with exclusive regioselectivity and generally excellent diastereo- and enantioselectivities. Expand
Catalytic enantioselective synthesis of alkenylhydrosilanes.
Among the several possible methods for the asymmetric synthesis of chiral silanes, desymmetrization of achiral silane A would be the most rational approach (Scheme 1). Expand
Hydrosilylation of Carbon–Carbon Multiple Bonds—Application in Synthesis and Materials Science
Abstract Hydrosilylation of alkenes and alkynes is the most fundamental and elegant method for laboratory and industrial synthesis of organosilicon molecular and macromolecular compounds, which canExpand
Enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles
A rhodium-catalyzed enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles that exhibit bright blue fluorescence, which would have potential application prospects in organic optoelectronic materials. Expand
Hydride Transfer Ring-Opening Polymerization of a Cyclic Oligomethylhydrosiloxane. Route to a Polymer of Closed Multicyclic Structure
The ring-opening polymerization of 2,4,6,8-tetramethyltetrahydro-cyclotetrasiloxane, DH4, in the presence of tris(pentafluorophenyl)borane, B(C6F5)3, has been studied in dilute toluene solution. TheExpand
Functionalized polysilalkylene siloxanes (polycarbosiloxanes) by hydrosilylation—Catalysis and synthesis
Polysilalkylene siloxanes or ‘hybrid silicones’ are a comparatively new class of polymeric materials combining the chemical properties of silicones and paraffins in a unique way. They can be used asExpand


A Stereoselective Approach to Optically Active Bifunctional 1,3-Dimethyl-1,3-diphenyldisiloxanes
Functionalized disiloxanes have attracted much attention as versatile synthetic intermediates in the preparation of disiloxane-containing polymers. In this report, a highly stereoselective (98% inv...
Elucidation of the Stereochemical Pathway to Isotactic Poly[(methylphenylsilylene)trimethylene] from Allylmethylphenylsilane
Elucidation of the Stereochemical Pathway to Isotactic Poly[(methylphenylsilylene)trimethylene] from Allylmethylphenylsilane
Synthesis of Poly(methylphenylsilylenetrimethylene) Rich in Isotacticity Characterized by 750 MHz 1H NMR
We report the first example of the synthesis of poly(methylphenylsilylenetrimethylene) rich in isotacticity by self-polyaddition of allylhydromethylphenylsilane
Chromatographic separation of asymmetric organosilicon compounds on cellulose and amylose stationary phases. The stereochemistry of functional transformation reactions
SummarySilicon compounds, especially silanes, have been separated on cellulose carbamate and amylose carbamate stationary phases. Reasonable recognition is achieved in the separation of organosiliconExpand
Substituent effects on 2-aza-5-hexynyl radical cyclization regiochemistry
Abstract Cyclizations of several N-acyl-2-aza-5-hexynyl radicals are described. The regiochemical course of these cyclizations depend on the nature of substituents at the alkyne terminus.
Preparations and Reactions of Functionalized Silyllithiums
Several types of α-alkoxy and α-amino substituted silyllithiums have been prepared as the first members of stable and/or well-characterizable functionalized silyllithiums. Described herein are newExpand
Tris(pentafluorophenyl)borane as a Superior Catalyst in the Synthesis of Optically Active SiO-Containing Polymers
Tris(pentafluorophenyl)borane was found to be an effective catalyst in the synthesis of optically pure and completely diisotactic phenyl- and naphthyl-substituted poly(siloxane)s by the reactionExpand
Stereospecific formation of optically active trialkylsilyllithiums and their configurational stability
Optically active trialkylsilyllithiums, (R)-(n-butyl)methylphenylsilyllithium (63% ee) and (S)-methyl(1-naphthyl)phenylsilyllithium (96% ee), were prepared by cleavage of the siliconsilicon bond ofExpand
Synthesis and self-assembly of styrene[1]dimethylsilaferrocenophane - methyl methacrylate pentablock copolymers
Well-defined pentablock copolymers of styrene[1]dimethylsilaferrocenophane - methyl methacrylate (PMMA-b-PFS-b-PS-b-PFS-b-PMMA) are synthesized using lithium naphthalide as initiator and aExpand
Selective Formation of Both Enantiomerically Pure Disilanes from One Fluorosilane Antipode with Silyllithium
Stereochemistry crossover from retention to inversion of configuration at about −20 °C was observed in the nucleophilic substitution of optically active (R)-fluoromethyl(1-naphthyl)phenylsilaneExpand