We report the reactions of catecholborane (HBcat; 1 ) with unsaturated and saturated NHCs as well as CAACMe. Mono‐NHC adducts of the type HBcat?NHC (NHC=nPr2Im, iPr2Im, iPr2ImMe, and Dipp2Im) were obtained by stoichiometric reactions of HBcat with the unsaturated NHCs. The reaction of CAACMe with HBcat yielded the B?H activated product CAACMe(H)Bcat via insertion of the carbine‐carbon atom into the B?H bond. The saturated NHC Dipp2SIm reacted in a 2:2 ratio yielding an NHC ring‐expanded product at room temperature forming a six‐membered ?B?C=N?C=C?N? ring via C?N bond cleavage and further migration of the hydrides from two HBcat molecules to the former carbene‐carbon atom. 相似文献
Sandia National Laboratories developed the DaMaGe Initiated Reaction (DMGIR) model to numerically predict weakly supported shock waves that generate an initiation at energy levels below
the shock-to-detonation transition (SDT) of an explosive. The DMGIR model couples the strain energy fluence contribution from
damage to the initiation process. It does not attempt to include all possible specific initiation mechanisms at the mesoscale,
but instead looks at cumulative damage incurred in the explosive through experimental calibration of a small number of material
constants. Both shock pressure (hydrostatic) and shear stress (deviatoric) are accounted for in the summation. The model was
designed to be robust and relatively simple to calibrate. The DMGIR model is implemented into the Sandia National Laboratories’
CTH shock wave and large deformation code. The model runs concurrently with the existing History Variable Reactive Burn (HVRB)
model currently used for shock initiation. 相似文献
A concise synthetic route to an immunomodulatory pentasaccharide, lacto-N-fucopentaose III (1) and its corresponding human serum albumin conjugate, is described. Key transformations of the strategy include two highly regio- and stereoselective glycosylations for the construction of disaccharide 10 and pentasaccharide 12, a Birch reduction for deprotection of benzyl ethers, and a UV-promoted radical addition of a thiol to an alkene for modification of the aglycone. 相似文献
Oxidative decarboxylation of N-acyl-α-amino acids with lead tetra-acetate followed by treatment with methanol provides a facile method for preparation of acyclic N-acyl-N,O-acetals, which can be used in asymmetric α-amidoalkylation reactions using trimethylsilyl cyanide as nucleophile. 相似文献
Reaction products from the ozonolysis of unsaturated lipids at gas–liquid interfaces have the potential to significantly influence the chemical and physical properties of organic aerosols in the atmosphere. In this study, the gas-phase dissociation behavior of lipid secondary ozonides is investigated using ion-trap mass spectrometry. Secondary ozonides were formed by reaction between a thin film of unsaturated lipids (fatty acid methyl esters or phospholipids) with ozone before being transferred to the gas phase as [M + Na]+ ions by electrospray ionization. Activation of the ionized ozonides was performed by either energetic collisions with helium buffer-gas or laser photolysis, with both processes yielding similar product distributions. Products arising from the decomposition of the ozonides were characterized by their mass-to-charge ratio and subsequent ion-molecule reactions. Product assignments were rationalized as arising from initial homolysis of the ozonide oxygen–oxygen bond with subsequent decomposition of the nascent biradical intermediate. In addition to classic aldehyde and carbonyl oxide-type fragments, carbon-centered radicals were identified with a number of decomposition pathways that indicated facile unimolecular radical migration. These findings reveal that photoactivation of secondary ozonides formed by the reaction of aerosol-bound lipids with tropospheric ozone may initiate radical-mediated chemistry within the particle resulting in surface modification.
For a class of non-uniformly hyperbolic interval maps, we study rates of escape with respect to conformal measures associated with a family of geometric potentials. We establish the existence of physically relevant conditionally invariant measures and equilibrium states and prove a relation between the rate of escape and pressure with respect to these potentials. As a consequence, we obtain a Bowen formula: we express the Hausdorff dimension of the set of points which never exit through the hole in terms of the relevant pressure function. Finally, we obtain an expression for the derivative of the escape rate in the zero-hole limit. 相似文献