A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of ...A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear a,13-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C-N bond to furnish a cascade double C-N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C-N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C-N bond activation of the allylic diamines.展开更多
Based on ANSYS FEM software, the distribution of residual stress in the diffusion bonding joints between Ti（ C,N） metallic ceramic/interlayer/4OCr steel was calculated and experimentally ver^ed. The results showed t...Based on ANSYS FEM software, the distribution of residual stress in the diffusion bonding joints between Ti（ C,N） metallic ceramic/interlayer/4OCr steel was calculated and experimentally ver^ed. The results showed that the trend on the distribution of residual stress field in the joints was not changed with the use of interlayer. The maximum residual stress was always located in metallic ceramic with area ranging from 1 mm to 4 mm to the interlayer. The maximum residual stress in the joints was also affected by diffusion temperature. The satellite pulse current during the initial stage on diffusion bonding can promote the formation of liquid film at the interface, by which diffusion temperature and loading pressure can be greatly decreased. The crack initiation was easily produced at the corner of Ti （ C, N） metallic ceramic close to the interlayer. If a higher residual stress produced in the joints, the crack was propagated into the whole ceramic.展开更多
To evaluate the effect of neutral C–H bond or electron pair of nitrogen atom with sp2hybridization（N（sp2）） involving into the same chemical environment for anion binding, two analogous tetracationic imidazolium m...To evaluate the effect of neutral C–H bond or electron pair of nitrogen atom with sp2hybridization（N（sp2）） involving into the same chemical environment for anion binding, two analogous tetracationic imidazolium macrocycles, namely cyclo[2]（2,6-bis-（1H-imidazol-1-yl）pyridine） [2]（1,3-dimethylenebenzene）（14＋）, and cyclo[2]（2,6-bis-（1H-imidazol-1-yl）pyridine）[2]（2,6-di methylenepyridine）（24＋）were studied in detail as small inorganic anion receptors. The vip anions with different shapes are Cl,N3, NO3, and H2PO4. The host–vip interactions were characterized via1 H NMR spectroscopy,electrospray ionization mass spectrometry（ESI-MS） and single crystal X-ray crystallography. The results implied that macrocyclic hosts with similar backbone but two distinct binding sites（14＋with neutral C–H vs. 24＋with N（sp2）） vary markedly in their response to anions, including the binding modes and association constants. The finding will serve to the construction of new anion receptors, even improve insights into the anion binding process in biology.展开更多
基金This research was supported by the National Natural Science Foundation of China （Nos. 21672199 and 21790333） and CAS Interdisciplinary Innovation Team.
文摘A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear a,13-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C-N bond to furnish a cascade double C-N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C-N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C-N bond activation of the allylic diamines.
基金The authors are grateful to the financial support for this research from National Natural Science Foundation of China （Grant No. 51175259） , Jiangsu Science and Technology Planning Project （No. BK2011494） and University Science Research Project of Jiangsu Province （ 11KJAd30005 ）.
文摘Based on ANSYS FEM software, the distribution of residual stress in the diffusion bonding joints between Ti（ C,N） metallic ceramic/interlayer/4OCr steel was calculated and experimentally ver^ed. The results showed that the trend on the distribution of residual stress field in the joints was not changed with the use of interlayer. The maximum residual stress was always located in metallic ceramic with area ranging from 1 mm to 4 mm to the interlayer. The maximum residual stress in the joints was also affected by diffusion temperature. The satellite pulse current during the initial stage on diffusion bonding can promote the formation of liquid film at the interface, by which diffusion temperature and loading pressure can be greatly decreased. The crack initiation was easily produced at the corner of Ti （ C, N） metallic ceramic close to the interlayer. If a higher residual stress produced in the joints, the crack was propagated into the whole ceramic.
基金financially supported by the National Natural Science Foundation of China (No. 21202199 to Han-Yuan Gong, and No. 21372258 to Li-Jin Xu)
文摘To evaluate the effect of neutral C–H bond or electron pair of nitrogen atom with sp2hybridization（N（sp2）） involving into the same chemical environment for anion binding, two analogous tetracationic imidazolium macrocycles, namely cyclo[2]（2,6-bis-（1H-imidazol-1-yl）pyridine） [2]（1,3-dimethylenebenzene）（14＋）, and cyclo[2]（2,6-bis-（1H-imidazol-1-yl）pyridine）[2]（2,6-di methylenepyridine）（24＋）were studied in detail as small inorganic anion receptors. The vip anions with different shapes are Cl,N3, NO3, and H2PO4. The host–vip interactions were characterized via1 H NMR spectroscopy,electrospray ionization mass spectrometry（ESI-MS） and single crystal X-ray crystallography. The results implied that macrocyclic hosts with similar backbone but two distinct binding sites（14＋with neutral C–H vs. 24＋with N（sp2）） vary markedly in their response to anions, including the binding modes and association constants. The finding will serve to the construction of new anion receptors, even improve insights into the anion binding process in biology.
