2857-97-8Relevant articles and documents
Redistribution equilibria of substituents between the methyl- and trimethylsilicon moieties
Moedritzer, Kurt,Van Wazer, John R.
, p. 1254 - 1257 (1966)
Scrambling equilibria resulting from the exchange of pairs of monofunctional substituents (halogen, methoxyl, methylthio, and dimethylamino) between the methyl- and trimethylsilicon moieties have been studied by proton nuclear magnetic resonance. Unexpect
N-H cleavage as a route to new pincer complexes of high-valent rhenium
Kosanovich, Alex J.,Shih, Wei-Chun,Ramírez-Contreras, Rodrigo,Ozerov, Oleg. V.
, p. 18532 - 18540 (2016)
A novel PNN-type pincer ligand has been accessed via imine reduction with LiAlH4 to provide the phosphine diamino proligand, PNHNH (1). The ligand, 1, as well as PNHP can be metallated directly, via N-H cleavage, with L2ReOX2(OEt) precursors to access six-coordinate (PNP)ReOCl2 (2) and (PNNH)ReOX2 (3-Cl, X = Cl; 3-Br, X = Br) in good yield. 3-Cl and 3-Br undergo dehydrohalogenation upon treatment with NEt3, furnishing the five-coordinate phosphine/diamido PNN-type compounds (PNN)ReOX (4-Cl, X = Cl; 4-Br, X = Br) in excellent yield, presenting as a mixture of rotameric diasteromers. The reversibility of this deprotonation, and the coordinative unsaturation of 4-Cl is shown in reactions with HCl(aq) and PMe3 providing 3-Cl and 4-PMe3, respectively. Treatment of 4-Cl with AgOAc, AgOTf, or NaHBEt3 lead to formation of (PNN)ReO(OAc) (4-OAc), (PNN)ReO(OTf) (4-OTf), and (PNN)ReO(H) (4-H), all isolated in excellent yields in varying diasteromeric ratios. The nature of the isomerism was analyzed based on solid-state structural studies and solution NMR data.
The First Gallium-Arsenic Compound containing a Single Ga3As Unit: Isolation and Crystal Structure of 3As (thf=tetrahydrofuran)
Wells, Richard L.,Shafieezad, Soheila,McPhail, Andrew T.,Pitt, Colin G.
, p. 1823 - 1824 (1987)
3As (thf=tetrahydrofuran), isolated from the products of the reaction of (Me3Si)3As with GaBr3, has been shown by X-ray crystallographic analysis to be the first example of a compound containing a single Ga3As unit.
STEPWISE CONVERSION OF OXIRANES TO ALLYLIC ALCOHOLS BY IODOTRIMETHYLSILANE AND DBU
Sakurai, Hideki,Sasaki, Koshi,Hosomi, Akira
, p. 2329 - 2332 (1980)
Iodotrimethylsilane, prepared from hexamethyldisilane and iodine, reacts smoothly with oxiranes to give (2-iodoalkoxy)trimethylsilanes which can be converted to allylic alcohols with DBU in good yields.The whole conversion can be carried out in one-pot operation.
A simple one-pot synthesis of methyltribromosilane
Pitcher, Michael W.,Bianconi, Patricia A.
, p. 1819 - 1822 (2007)
A simple one-pot synthesis of methyltribromosilane has been developed. The straightforward reaction of a slight excess of silicon tetrabromide with one equivalent of powdered methyllithium in refluxing pentane produces methyltribromosilane in high yields.
C3-Heteroaroyl cannabinoids as photolabeling ligands for the CB2 cannabinoid receptor
Dixon, Darryl D.,Tius, Marcus A.,Thakur, Ganesh A.,Zhou, Han,Bowman, Anna L.,Shukla, Vidyanand G.,Peng, Yan,Makriyannis, Alexandros
supporting information; experimental part, p. 5322 - 5325 (2012/09/07)
A series of tricyclic cannabinoids incorporating a heteroaroyl group at C3 were prepared as probes to explore the binding site(s) of the CB1 and CB2 receptors. This relatively unexplored structural motif is shown to be CB2 selective with Ki values at low nanomolar concentrations when the heteroaromatic group is 3-benzothiophenyl (41) or 3-indolyl (50). When photoactivated, the lead compound 41 was shown to successfully label the CB2 receptor through covalent attachment at the active site while 50 failed to label. The benzothiophenone moiety may be a photoactivatable moiety suitable for selective labeling.
Homolytic reactions of N-bromohexamethyldisilazane with trialkyl(phenylalkoxy) derivatives of silicon and tin
Rakhlin,Podgorbunskaya,Voronkov
experimental part, p. 930 - 935 (2011/01/09)
The main product of the photoinduced reaction of N- bromohexamethyldisilazane with trialkyl-(benzyloxy)derivatives of silicon and tin R3MO(CH2)nPh (R = Me, Et; M = Si, Sn; n = 1) is N,N-dibenzylidene-C-phenylmethanediamine (hydrobenzamide). For M = Si, with increase of the length of the methylene chain between the oxygen atom and the phenyl group (n = 2, 3), the similar reaction affords the product of bromination of the benzylic carbon atom R3MO(CH2) n-1CHBrPh. For M = Sn, the reaction results in the formation of 2-phenyloxacycloalkanes PhCHO(CH2)n-1. Pleiades Publishing, Ltd., 2010.
An efficient large-scale synthesis of gemcitabine employing a crystalline 2, 2-difluoro-α-ribofuranosyl bromide
Chang, Young-Kil,Lee, Jaeheon,Park, Gha-Seung,Lee, Moonsub,Park, Chul Hyun,Kim, Han Kyong,Lee, Gwansun,Lee, Bo-Young,Baek, Ju Yuel,Kim, Kwan Soo
experimental part, p. 5687 - 5691 (2010/09/18)
An efficient large-scale synthesis of gemcitabine was achieved without chromatography or fractional crystallization. The key steps include stereospecific conversion of a novel β-ribofuranosyl phosphate into a highly crystalline a-ribofuranosyl bromide and coupling of the α-ribofuranosyl bromide and trime- thylsilyl cytosine to produce a β-nucleoside. p-Phenylbenzoyl group was introduced for the protection of one of hydroxy groups in order to enhance the crystallinity of intermediates. Continuous removal of trimethylsilyl bromide, generated during the coupling reaction, by distillation from the reaction medium substantially enhanced the β-selectivity of the crucial coupling reaction.
Spin chemistry of organometallic compounds 5. Interaction of N-bromohexamethyl disilazane with substituted silyl hydrides
Taraban, Marc B.,Rakhlin, Vladimir I.,Volkova, Olga S.,Podgorbunskaya, Tatyana A.,Kuibida, Leonid V.,Mirskov, Rudolf G.,Leshina, Tatyana V.,Sherstyannikova, Larisa V.,Voronkov, Mikhail G.
scheme or table, p. 3815 - 3820 (2009/04/06)
Reaction of N-bromohexamethyl disilazane (Me3Si)2NBr with substituted triorganyl silanes R1R2R3SiH results in asymmetric disilazanes Me3SiNHSiR1R2R3 and bromination product, bromotrimethyl silane Me3SiBr. The reaction has demonstrated an unusual dependence on specific solvation. In benzene, bromination occurs immediately after mixing of the reagents, while in cyclohexane, the reaction products are formed only under UV-irradiation. Application of photoinduced CIDNP method has shown that the mechanism of bromination of triorganyl silanes is comprised of a series of consecutive radical stages involving N-centered disilazanyl (Me3Si)2N{radical dot} and Si-centered silyl R1R2R3Si{radical dot} radicals.
A convenient one-pot preparation of stable equivalents of cyclobutane-1,2-dione and cyclobutanetrione
Deguest, Geoffrey,Bischoff, Laurent,Fruit, Corinne,Marsais, Francis
, p. 841 - 847 (2008/09/17)
A very short, high-yielding, one-pot procedure has been developed for the preparation of half-protected cyclobutane-1,2-dione. This compound is much more stable than cyclobutane-1,2-dione itself and allowed further transformation to give diprotected cyclobutanetrione equivalents. Copyright Taylor & Francis Group, LLC.
