(E)-rich 1-Bromo-2-butene preferentially caused γ-syn-allylation of aldehydes with tin(II) iodide and tetrabutylammonium bromide (or iodide) in THF-H2O or 1,3-dimethyl-2-imidazolidinone-H2O to produce 1-substituted syn-2-methyl-3-buten-1-ols.

Tryptophan (Trp) catabolizing enzymes play an important and complex role in the development of cancer. Significant evidence implicates them in a range of inflammatory and immunosuppressive activities. Whereas inhibitors of indoleamine 2,3-dioxygenase-1 (IDO1) have been reported and analyzed in t...

RésuméLes condensations d'amines sur le chloro-1 cycloheptène en présence de base complexe (NaNH2-t-BuONa) permettent d'obtenir des mélanges d'énamines et d'un dimère du cycloheptadiène-1,2. Dans les mêmes conditions, les chloro-2 et chloro-3 bicyclo [3,2,1] octènes...

Reactions of 1-halocycloheptenes with KO-t-Bu in DMSO and THF were studied. The principal products obtained could be accounted for on the basis of two competing dehydrohalogenation mechanisms. These are: dehydrohalogenation across the C1-C2 bond to give cycloheptyne; and dehydrohalogenation acro...

RésuméLa condensation en milieu aprotique des énolates de la diisopropyl et de la méthyl phényl cétone sur le chloro-1 cycloheptène, conduit essentiellement à des bicyclo [5.2.0] nonène-1 ols-8. L'orientation de ces réactions en fonction du solvant est étudiée et le mécanisme d...

RésuméLa condensation, en milieu aprotique, des énolates de cétones alicycliques sur le chloro-1 cycloheptène conduit, en présence de bases, aux tricyclo[7.n.0.02,8alcène-7 ols-1. L'intermédiaire de ces réactions est probablement le cycloheptadiène-1,2. L'orientation de ces r...

Alternate lithiation and reaction with ClSiMe3 of 2,6-dimethylpyridine gave the lithium derivatives of pyridine substituted at the 2- and 6-positions by mono- or bis(trimethylsilyl)methyl groups. The relative ease of formation of these compounds is discussed and compared to their reactivity with...

The synthesis and ring cleavage reactions of 2-alkyl-2-trimethylsilylmethyl-1.3-dithianes are described. The cleavage lead to 2-alkylthio-1-vinylsilanes and, via silicon migration, to 2-[3-alkylthio-3-(trimethylsilyl)propylthio]-1-alkenes.

Phenyl(1,1-dichloroethyl)mercury has been prepared via 1,1-dichloroethyllithium and evaluated as a potential CH3CCl transfer agent. Although this mercurial reacted with triethylsilane to give Et3SiCHClCH3 (35%) and with allyltrimethylsilane to give 1-chloro-1-methyl-2-(trimethylsilylmethyl)cyclo...

Static conformations and the dynamic behavior of the radicals (MCH2)2ĊX (where M = SiR3, GeR3, or SnR3); X = H, CH3, or OSiMe3) have been investigated by ESR. At the preferred conformation, the two metal groups almost eclipse the singly-occupied carbon p-orbital and are located on the opposite s...

Carbon-13 and proton NMR spectra have been determined for organothallium (III) derivatives of the types RTlX2 and R2 TlX (R  (CH3)3CCH2 or (CH3)3SiCH2; X  Cl, Br or O2CCH(CH3)2). The dependence of coupling of 13C and 1H to thallium on the number and nature of R groups is discussed in terms o...

The compounds [(Me3SiCH2)3Sn]2M, where M = Hg and Cd, are essentially more thermally stable than the compounds prepared earlier with SnMSn groupings. Apparently this is a result of the stabilizing effect of teh Me3SiCH2 substituents. The reactivity of teh stannylmercury compound does not differ ...

Tris(trimethylsilylmethyl)aluminium, made from bis(trimethylsilylmethyl)mercury and aluminium foil, is a colourless inflammable liquid, which appears to give a mixture of monomeric and dimeric species in benzene. It reacts with methylamine to yield the dimeric amido derivative [(Me3SiCH2)2AlNHMe]2.

Reactions between bis(trimethylsilyl)methyllithium and the chlorides ECl3 (E = B or Al) yield the di[bis(trimethylsilyl)methyl] derivatives [(Me3Si)2CH]2ECl. The boron compound may be converted by compounds HX (X = OH, NH2, NMe2) in the presence of bases to compounds [(Me3Si)2CH]2BX but the alum...

For the purpose of obtaining orally potent VLA-4 inhibitors, we have carried out structural modification of the (N′-phenylureido)phenyl group in compound 1, where the group was found to be attributed to poor pharmacokinetic profile in our previous research. Through modification, we have identif...

Mixtures consisting of five equivalents each of borane · methyl sulfide and boron trifluoride etherate per equivalent of acetal or five equivalents of various amine-borane complexes and 10 equivalents of boron trifluoride etherate readily accomplished reductive cleavage of the glycosidic linkag...

In certain conditions, the action of borane dimethyl sulfide (BMS) with aromatic carboxylic acids leads to the corresponding methyl derivatives or, in the presence of BF3, to the benzyl dimethyl sulphonium salts.

A 1-isopropyl-3-phospholene 1-oxide was prepared and the two enantiomers were isolated from the racemate by resolution using optically active TADDOL derivatives or the acidic Ca2+ salts of (−)-O,O-diaroyl-(2R,3R)-tartaric acids. The single crystal X-ray structure of the 1-isopropyl-3-phospholene...

On reacting the simple 1,2-amino alcohol: 2-amino-2-methylpropan-1-ol, with borane methyl sulfide (BMS), the expected five member oxazaborolidine ring is not obtained. Instead, two polycyclic structures with trigonal boron atoms 6 and 7 were obtained, and their structure were determined by X-ray...

(5-Methyl-[1,3,5]-dithiazinan-2-yl)diphenylphosphine (1) and its oxide (4), sulphide (5) and selenide (6), bis(5-methyl-[1,3,5]-dithiazinan-2-yl)phenylphosphine (2) and its sulphide (7) and selenide (8) and tris(5-methyl-[1,3,5]-dithiazinan-2-yl)phosphine (3) and its sulphide (9) and selenide (1...