91118-75-1Relevant academic research and scientific papers
A HIGHLY STEREOSELECTIVE ROUTE TO 2-ALKENYLTRIMETHYLSILANES
Shimizu, Nobujiro,Shibata, Fumihiro,Tsuno, Yuho
, p. 1593 - 1594 (1985)
1,2-Epoxy-1,3-bis(trimethylsilyl)propane reacts with various Grignard reagents (RMgX) to give 1-R-2,3-bis(trimethylsilyl)-1-propanols which upon olefination with NaH or with BF3Et2O give the corresponding (Z) or (E)-2-alkenyltrimethylsilanes in moderate t
Stereoselective Synthesis of (E)- and (Z)-2-Alkenyltrimethylsilanes from 1,2-Epoxy-1,3-bis(trimethylsilyl)propane
Shimizu, Nobujiro,Imazu, Sachiko,Shibata, Fumihiro,Tsuno, Yuho
, p. 1122 - 1128 (2007/10/02)
Stereoselective synthesis of various (E)- and (Z)-2-alkenyltrimethylsilanes (RCH=CHCH2SiMe3; R=Me, Et, n-Bu, i-Pr, c-hexyl, t-butyl, and phenyl) has been accomplished by a reaction of 1,2-epoxy-1,3-bis(trimethylsilyl)propane with Grignard reagents (RMgX) followed by subsequent Peterson olefination reactions of resulting 1,2-bis(trimethylsilyl)-3-alkanols ; the acid (BF3OEt2 or HClO4)-catalyzed olefination yields the (E)-isomer, while the base (KH or NaH)-induced olefination yields the (Z)-isomer in more than 95 percent stereochemical purity in most cases.
Regioselective Synthesis of Allyltrimethylsilanes from Allylic Halides and Allylic Sulfonates. Application to the Synthesis of 2,3-Bis(trimethylsilyl)alk-1-enes
Smith, Janice Gorzynski,Drozda, Susan E.,Petraglia, Susan P.,Quinn, Nina R.,Rice, Elizabeth M.,et al.
, p. 4112 - 4120 (2007/10/02)
The preparation of allyltrimethylsilanes by regioselective pathways is described.Treatment of (E)-1-chloro-2-alkenes with a reagent prepared from 1 equiv each of trimethylsilyllithium and copper(I) iodide in hexamethylphosphoramide to presumably form a (trimethylsilyl)copper reagent affords 3-(trimethylsilyl)-1-alkenes in good to excellent yields with a high regioselectivity.Treatment of these same 1-chloro-2-alkenes with (trimethylsilyl)lithium alone without added copper(I) iodide yields only (E)-1-(trimethylsilyl)-2-alkenes.A single allylic halide thus yields two regioisomeric allyltrimethylsilanes by proper choice of reaction conditions.The reaction of a variety of allylic sulfonates with (trimethylsilyl)copper has also been investigated.The mesylates of 2 deg and 3 deg allylic alcohols yield mixtures of isomeric allyltrimethylsilanes in which the 1-(trimethylsilyl)-2-alkenes predominate.With geraniol, the mesylate was prepared in situ and allowed to react with (trimethylsilyl)copper to afford two isomeric allyltrimethylsilanes in which the 3-(trimethylsilyl)-1-alkene predominates.Finally, these reactions have also been used to prepare a variety of 2,3-bis(trimethylsilyl)alk-1-enes, a class of unsaturated organosilanes which has received little attention in the literature.
