16722-09-1Relevant academic research and scientific papers
Vinylidene Homologation of Boronic Esters and its Application to the Synthesis of the Proposed Structure of Machillene
Fordham, James M.,Grayson, Matthew N.,Aggarwal, Varinder K.
supporting information, p. 15268 - 15272 (2019/10/21)
Alkenyl boronic esters are important reagents in organic synthesis. Herein, we report that these valuable products can be accessed by the homologation of boronic esters with lithiated epoxysilanes. Aliphatic and electron-rich aromatic boronic esters provided vinylidene boronic esters in moderate to high yields, while electron-deficient aromatic and vinyl boronic esters were found to give the corresponding vinyl silane products. Through DFT calculations, this divergence in mechanistic pathway has been rationalized by considering the stabilization of negative charge in the C?Si and C?B bond breaking transition states. This vinylidene homologation was used in a short six-step stereoselective synthesis of the proposed structure of machillene, however, synthetic and reported data were found to be inconsistent.
Method for synthesizing 2-phenyl-2-trimethylsilyl acetyl chloride from trimethyl (vinyl) silane
-
Paragraph 0008-0010, (2018/05/01)
The invention relates to a method for synthesizing 2-phenyl-2-trimethylsilyl acetyl chloride from trimethyl (vinyl) silane, to mainly solve the technical problem that an industrial synthesis method ofthe compound is in shortage. The method comprises the following three steps: step 1, dissolving trimethyl(vinyl)silane in dichloromethane, and adding 3-chloroperoxybenzoic acid at a low temperature for reaction to obtain trimethyl (2-epoxyethyl)silane; step 2, dissolving phenyl magnesium bromide and cuprous cyanide in isopropyl ether at a low temperature, and adding trimethyl(2-epoxyethyl)silanefor reaction to generate 2-phenyl-2-trimethylsilyl ethanol; step 3, carrying out a reaction of a tetrahydrofuran solution of the 2-phenyl-2-trimethylsilyl ethanol under the condition with triethylamine and triphosgene to generate 2-phenyl-2-trimethylsilyl acetyl chloride.
CARBON DIOXIDE ABSORBENT AND METHOD OF USING THE SAME
-
Page/Page column 32, (2011/02/24)
In accordance with one aspect, the present invention provides an amino-siloxane composition comprising at least one of structures I, II, III, IV or V said compositions being useful for the capture of carbon dioxide from gas streams such as power plant flu
The (2-Phenyl-2-trimethylsilyl)ethyl-(PTMSEL)-Linker in the Synthesis of Glycopeptide Partial Structures of Complex Cell Surface Glycoproteins
Wagner, Michael,Dziadek, Sebastian,Kunz, Horst
, p. 6018 - 6030 (2007/10/03)
The (2-phenyl-2-trimethylsilyl)ethyl-(PTMSEL) linker represents a novel fluoride-sensitive anchor for the solid-phase synthesis of protected peptides and glycopeptides. Its cleavage is achieved under almost neutral conditions using tetrabutylammonium fluo
The (2-phenyl-2-trimethylsilyl) ethyl-(PTMSEL) linker - A novel linker for the solid-phase synthesis of protected peptides and glycopeptides cleavable with fluoride
Wagner, Michael,Kunz, Horst
, p. 317 - 321 (2007/10/03)
Suitable for the immobilization of carboxylic acids, the (2-phenyl-2-trimethylsilyl)ethyl linker was developed as a novel, fluoride-sensitive anchor. Cleavage with tetrabutylammonium fluoride (TBAF) trihydrate in CH2Cl2 under almost
(2-Phenyl-2-trimethylsilyl)ethyl (PTMSE) esters - A novel carboxyl protecting group
Wagner, Michael,Kunz, Horst
, p. 400 - 402 (2007/10/03)
A novel silicon-containing protecting group based on the known 2- (trimethylsilyl)ethyl system has been developed for the protection of the carboxylic group, e.g. in peptide chemistry. The new protecting group can be cleaved by treatment with tetra-n-butylammonium fluoride much more rapidly than the known 2-(trimethylsilyl)ethyl group, leading to less side reactions.
The (2-phenyl-2-trimethylsilyl)ethoxycarbonyl (Psoc) group - A novel amino protecting group
Wagner,Heiner,Kunz
, p. 1753 - 1756 (2007/10/03)
A novel silicon containing protecting group has been developed based on the known 2-(trimethylsilyl)ethyl system. The new protecting group is cleaved under very mild conditions by treatment with tetra-n-butylammonium fluoride in CH2Cl2 much more rapidly than the 2-(trimethylsilyl)ethoxycarbonyl group, leading to less side reactions.
Regiospecific Synthesis of 1-Silyl Substituted 1,4-Dienes
Schaumann, Ernst,Kirschning, Andreas
, p. 419 - 421 (2007/10/02)
The reaction of epoxysilanes with lithiated allylsilanes gives predominantly α-silyl-substituted alcohols (3) which are convenient precursors for the preparation of 1-silyl-substituted 1,4-dienes.
AN EFFICIENT METHOD FOR PREPARATION OF TRIMETHYLSILYL ETHYLENE OXIDE AND SOME OTHER TRIMETHYLSILYL OXIRANES
Jankowski, P.,Masnyk, M.,Wicha, J.
, p. 873 - 880 (2007/10/02)
Trimethylsilyl ethylene oxide and other α,β-epoxysilanes were obtained from corresponding (trimethylsilyl)alkenes by an one-pot procedure involving successive treatment with N-bromosuccinimide and aqueous sodium hydroxide.
Organosilicon compounds with functional groups proximate to silicon. XVII. Synthetic and mechanistic aspects of the lithiation of α,β-epoxyalkylsilanes and related α-heterosubstituted epoxides
Eisch, John J.,Galle, James E.
, p. 293 - 314 (2007/10/02)
A series of α-heterosubstituted epoxides, , has been found to undergo lithiation in the temperature range of -75 to -115 deg C at the C-H bond of the epoxide.The substituent Z could be Me3Si, Ph3Si, n-Bu3Sn, Ph3Sn, PhSO2, (OEt)2PO and Ph; the groups R and R' were H, Ph and n-C6H13; and the lithiating reagents were n-butyllithium, t-butyllithium and lithium diisopropylamide in donor media of THF or TMEDA.The lithiation occurs with retention of configuration and the resulting lithio-epoxide is unstable above 0 deg C, decomposing in a carbenoid manner.The lithiation is facile except for compounds where Z and R (an alkyl or aryl) are cis-oriented; where Z = R3Sn, lithiation occurs by tin-lithium, rather than hydrogen-lithium, exchange.The lithio-epoxides thereby generated can be quenched with various reagents to yield epoxides where the epoxide H has been replaced by D, Me3Sn, R, RCO and COOH.The utility of this procedure in organic synthesis is emphasized.Finally, the possible explanations for the acidity of such α-heterosubstituted epoxides and for the relative stability of the derived lithio-epoxides are considered and assessed.
