Stereoselective formation of phenylthio groups substituted 1-metalla-3-titanacyclobutanes
摘要:
Desulfurizative titanation of group 14 metal compounds bearing two or four bis(phenylthio)methyl groups with the low-valent titanium reagent Cp2Ti[P(OEt)(3)](2) produced phenylthio groups substituted 1-metalla-3-titanacyclobutanes stereoselectively. The molecular structures of the titanacycles were unambiguously confirmed by X-ray diffraction analysis. (c) 2010 Elsevier B.V. All rights reserved.
o-1-cycloalkenes with titanocene(II)-triethyl phosphite complex, reacted with styrene derivatives to produce (E)-1,4-dienes. Their reaction with vinyl-borane and -silane also produced 1-boryl- and silyl-1,4-dienes, which were transformed into 1-substituted 1,4-dienes through the palladium(0)-catalyzed or copper(I)-promoted reaction with organic halides.
Preparation of silyl polyenol ethers by carbonyl olefination of silyl esters
作者:Takeshi Takeda、Tatsuya Fukada、Akira Tsubouchi
DOI:10.1016/j.tetlet.2014.01.040
日期:2014.2
Silyl enol ethers were produced by the carbonyl olefination of silylesters with titanium carbene complexes generated by the desulfurizative titanation of thioacetals. The regioselective preparation of silyl dienol and trienol ethers has been achieved by using unsaturated silylesters and thioacetals.
[2 + 2 + 1] Cycloaddition between Alkynes, Acrylates, and Titanocene(II): Regioselective Formation of 5-Alkoxycarbonyltitanacyclopent-2-enes and Their Addition to Carbonyls
5-Alkoxycarbonyltitanacyclopent-2-enes were produced regioselectively by the [2 + 2 + 1] cycloaddition between alkynes, acrylates, and titanocene(II) reagent Cp 2 Ti[P(OEt) 3 ] 2 . Although the titanacycles were inactive toward carbonyl compounds, their addition proceeded in the presence of titanocene(II).
通过炔烃、丙烯酸酯和二茂钛 (II) 试剂 Cp 2 Ti[P(OEt) 3 ] 2 之间的 [2 + 2 + 1] 环加成反应,区域选择性地制备了 5-烷氧基羰基钛环戊-2-烯。尽管钛环对羰基化合物无活性,但它们的加成是在二茂钛 (II) 存在下进行的。
Synthesis of carbocycles and heterocycles by the titanocene(II)-promoted reactions of thioacetals
The preparation of carbocyclic and heterocyclic compounds by the low-valent titanium species-promoted intramolecular reactions of thioacetals was studied. The cyclization of thioacetals having an olefin moiety proceeded with the loss of terminal olefin carbon to produce the corresponding five-, six-, and seven-membered cycloalkenes when they were treated with the low-valent titanium species Cp2Ti[P(OEt)(3)](2). This method has been successfully applied to the syntheses of cyclic unsaturated amines and ethers. When S-[3,3-bis (phenylthio) propyl] thioalkanoates were treated with the low-valent titanium species, the intramolecular carbonyl olefination proceeded to produce 5-substituted 2,3-dihydrothiophenes. (C) 2000 Elsevier Science Ltd All rights reserved.