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Chalcogenide-Lewis Acid Mediated Reactions of Electron-Deficient Alkynes With Aldehydes

Chalcogenide-Lewis Acid Mediated Reactions of Electron-Deficient Alkynes With Aldehydes

Sayaka Kinoshita, Hironori Kinoshita, Tatsunori Iwamura, Shin-Ichi Watanabe, Tadashi Kataoka

Chemistry. 2003 Apr 4;9(7):1496-502.

PMID: 12658646

Abstract:

Reactions of but-3-yn-2-one (2) with aldehydes 1 in the presence of a Lewis acid and dimethyl sulfide (3 a) predominantly gave (E)-alpha-(halomethylene)aldols 4-5 in high yields, while reactions of methyl propiolate (6 a) mainly afforded (Z)-3-halogeno-2-(hydroxymethyl)acrylates 7-8 in low to moderate yields. A reaction of dimethyl acetylenedicarboxylate (10) with 1 a in the presence of TiCl(4) and 1,1,3,3-tetramethylthiourea (3 c) produced maleate (E)-11 (40 %) and butenolide 12 (40 %). When a reaction of 6 a with 1 a was carried out in the presence of TiBr(4) and 3 a (0.2 equiv) at -20 degrees C for 60 h, 3-(methylthio)-2-(hydroxyalkyl)acrylate 9 a was obtained in an 8 % yield. Experiments were conducted in order to elucidate the formation mechanism of 9 a, and it was made clear that 9 a was formed via the processes of the Michael addition of sulfide 3 a to alkynoate 6 a and an aldol reaction with 1 a and demethylation.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP17741605	3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-Heneicosafluorododecyl acrylate		17741-60-5	Price

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