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101.
The development of a one-pot tandem intramolecular conjugate addition/nucleophilic acyl substitution using samarium(II) iodide is reported. The reaction relies on the reagent’s unique ability to mediate both radical and anionic pathways, which are likely integral to the mechanism of this transformation. The tricyclic hemiacetal product was formed in good yield, with excellent diastereoselectivity, and its structure was verified by X-ray crystallographic analysis. 相似文献
102.
103.
Nimitsiriwat N Marshall EL Gibson VC Elsegood MR Dale SH 《Journal of the American Chemical Society》2004,126(42):13598-13599
In an unprecedented transformation, amide ligands are found to attack the imine carbon centers of tridentate Schiff base ligands attached to tin. The process is reversible, and the resultant (masked) amide species can be exploited as latent single-site initiators for the controlled polymerization of rac-lactide. 相似文献
104.
Workman JA Garrido NP Sançon J Roberts E Wessel HP Sweeney JB 《Journal of the American Chemical Society》2005,127(4):1066-1067
The first examples of highly enantioselective [2,3]-sigmatropic rearrangements of acyclic allylic ammonium ylids are reported. Thus, a range of N-{2'-[(N'-allyl-N',N'-dialkyl)ammonium]}acetyl camphor sultams undergo rearrangement at 0 degrees C in DME solution with high diastereofacial control (up to 99:1 dr) to give allylglycines in generally high yield. The power of the method has been demonstrated in a rapid and efficient synthesis of (R)-allyl glycine. 相似文献
105.
Molecular Replacement Studies of Cucurmosin from Cucurbita Moschata:Structure Homology with Trichosanthin 总被引:2,自引:0,他引:2
1 INTRODUCTION Many plants contain proteins that are capable of inactivating ribosomes and therefore are called ribosome-inactivating proteins or RIPs[1]. RIPs are RNA N-glycosidases that inactivate ribosomes through a site-specific deadenylation of the large ribosomal RNA[2, 3]. RIPs are also capable of inactivating many nonribosomal nucleic acid substrates and can be considered as polynucleotide: adenosine glycosidases[4~6]. There are two types of RIPs: type I, single chain pr… 相似文献
106.
Nicola M Howarth W.Edward LindsellEuan Murray Peter N Preston 《Tetrahedron letters》2003,44(44):8089-8092
The adenine, cytosine and thymine peptide nucleic acid (PNA) monomers and PNA T10 oligomers bearing either a diacetylenic or stearoyl moiety at the N- or C-terminus have been successfully prepared. The resulting thymine monomeric and T10-mer derivatives have been subsequently incorporated into polydiacetylene-containing liposomes. 相似文献
107.
Thermal decomposition of RDX from reactive molecular dynamics 总被引:1,自引:0,他引:1
Strachan A Kober EM van Duin AC Oxgaard J Goddard WA 《The Journal of chemical physics》2005,122(5):54502
We use the recently developed reactive force field ReaxFF with molecular dynamics to study thermal induced chemistry in RDX [cyclic-[CH(2)N(NO(2))](3)] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition that increases with decreasing density and shows an Arrhenius temperature dependence. These characteristic timescales are in reasonable quantitative agreement with experimental measurements in a similar energetic material, HMX [cyclic-[CH(2)N(NO(2))](4)]. Our simulations show that the equilibrium population of CO and CO(2) (as well as their time evolution) depend strongly of density: at low density almost all carbon atoms form CO molecules; as the density increases larger aggregates of carbon appear leading to a C deficient gas phase and the appearance of CO(2) molecules. The equilibrium populations of N(2) and H(2)O are more insensitive with respect to density and form in the early stages of the decomposition process with similar timescales. 相似文献
108.
Edward Witten 《Communications in Mathematical Physics》1985,100(2):197-229
A general formula for global gauge and gravitational anomalies is derived. It is used to show that the anomaly free supergravity and superstring theories in ten dimensions are all free of global anomalies that might have ruined their consistency. However, it is shown that global anomalies lead to some restrictions on allowed compactifications of these theories. For example, in the case of O(32) superstring theory, it is shown that a global anomaly related to 7(O(32)) leads to a Dirac-like quantization condition for the field strength of the antisymmetric tensor field.Related to global anomalies is the question of the number of fermion zero modes in an instanton field. It is argued that the relevant gravitational instantons are exotic spheres. It is shown that the number of fermion zero modes in an instanton field is always even in ten dimensional supergravity.Supported in part by NSF Grant No. PHY80-19754 相似文献
109.
Rosenberg Edward Freeman William Carlos Zinnia Hardcastle Kenneth Yong Jin Yoo Milone Luciano Gobetto Roberto 《Journal of Cluster Science》1992,3(4):439-457
The general relationships between trinuclear cluster reactivity and the ligand dynamical processes in these systems are explored. Three specific mechanistic studies are presented: (1) the rate and stereochemistry of ligand addition to 3-imidoyl complexes, (2) the factors influencing the rate of carbon-hydrogen bond activation in 3-alkyne complexes, and (3) the origin of anomalously large kinetic deuterium isotope effect in metal to ligand and ligand to metal hydrogen transfer in trinuclear and binuclear complexes. In all three cases, the current state of the mechanistic studies are summarized and the possible rate of specific ligand dynamical processes in controlling the mechanism are put forth. 相似文献
110.
Edward E. Flagg Donald L. Schmidt 《Journal of polymer science. Part A, Polymer chemistry》1970,8(1):1-14
Poly[tris(diorganophosphinato)alanes], [Al(OPRR′O)3]n, were synthesized in which the organic moieties (R,R′) contained from one to eighteen carbon atoms. Polymeric properties depended upon the organic moieties; polymers were fusible, tractable, and flexible when the organic moieties contained six or more carbon atoms. Soluble polymers were prepared by using mixtures of symmetrical and unsymmetrical phosphinates. One polymer, poly{bis[n-butyl(benzyl)phosphinato]di-n-octylphosphinatoalane}, exhibited a degree of polymerization greater than 1000 and an exceptionally high intrinsic viscosity of 37 dl/g. The properties of the different polymers are discussed, and feasible structures are proposed. 相似文献