81113-09-9Relevant articles and documents
Electrogenerated Acid-Catalyzed Reactions of Acetals, Aldehydes, and Ketones with Organosilicon Compounds, Leading to Aldol Reactions, Allylations, Cyanations, and Hydride Additions
Torii, Sigeru,Inokuchi, Tsutomu,Takagishi, Sadahito,Horike, Hirofumi,Kuroda, Hideki,Uneyama, Kenji
, p. 2173 - 2188 (2007/10/02)
Exquisite use of electrogenerated acid (EG acid) in the silicon-mediated acid-catalyzed reactions; e.g., aldol reactions, allylations, cyanations, and hydride additions is described.The aldol reaction of acetals 1 with enol trimethylsilyl ethers 3 and 1,2-bis(trimethylsiloxy)alkenes 4 gives the corresponding adducts 5 and 6, respectively.The reaction proceeds smoothly with EG acid derived from perchlorate salts such as LiClO4, n-Bu4NClO4, and Mg(ClO4)2 in dichloromethane using platinum electrodes.The amount of electricity required to complete the reaction implies a cationic process which is mediated by the trimethylsilyl moiety.This aldol reaction is further developed with unprotected carbonyl compounds 2 with 3, giving the trimethylsilyl ethers of the adducts 7.Further utility of this EG acid as a catalyst for a chain reaction is exemplified by the successful application in the following conversions: (1) The allylation of acetals 1 with allyltrimethylsilane (8) to give 9, (2) the cyanation of acetals 1 and unmasked 2 with trimethylsilyl cyanide (10) to give 11, 12, and 13, and (3) the hydride addition of acetals 1 with triethylsilane (14) to give 15.
SYNTHESE ET REACTIVITE CATHODIQUE DES NITRILES α INSATURES-lV. ALKYL(ARYL)OXY-2 PHENYL-3 PROPENE NITRILES.
Cariou, M.,Mabon, G.,Guillanton, G. Le,Simonet, J.
, p. 1551 - 1558 (2007/10/02)
A one-pot synthesis of 2-alkyl(aryl)oxy-3-phenyl-propenonitriles, including silica gel chromatographic separation E and Z-isomers, is described.The attribution of the configurations is carried out by application of Tobey's rule from the chemical shifts of the vinylic protons.These activated olefins do not undergo cathodic coupling, but electrochemical carbon-oxygen bond cleavage.The relative stability of E and Z forms is reported.
2-ALKOXY AND 2,2-DIALKOXY NITRILES FROM ACETALS AND ORTHOESTERS --- EXCHANGE OF ALKOXY INTO CYANO GROUP BY MEANS OF CYANOTRIMETHYLSILANE
Utimoto, Kiitiro,Wakabayashi, Yukio,Shishiyama, Yuho,Inoue, Masaharu,Nozaki, Hitosi
, p. 4279 - 4280 (2007/10/02)
Title transformation is accomplished by the catalytic action of SnCl2 or BF3*OEt2.Lithio derivative of 2,2-dimethoxyacetonitrile is used as synthetic equivalent of methyl lithioformate.