The enamines, iminium ions, and oxazolidinones are thought to be the key intermediates in the proline-catalyzed reactions of aldehydes or ketones, but there is an extensive contro- versy about their roles. Here, the c...The enamines, iminium ions, and oxazolidinones are thought to be the key intermediates in the proline-catalyzed reactions of aldehydes or ketones, but there is an extensive contro- versy about their roles. Here, the corresponding transition states connecting any two of the three kinds of species are located at the wB97XD/6-311＋＋G＊＊ level of theory. The calcula- tions demonstrate that the oxazolidinones are the predominant species in both the gas phase and solvents; there exists tautomeric equilibrium among these species and the equilibriums are controlled by the employed solvents and temperature in the reaction. These results demonstrate that the concentration and role of the mentioned species are controlled by the employed solvent and temperature. A new reaction pathway is presented herein for the trans- formation between iminium ions and oxazolidinones through iminium ion-water complex and oxazolidinone-water complex. The calculations demonstrate that the rate-limiting step in proline-catalyzed Mannich reaction between acetaldehyde/keteones and N-Boc imines is the formation of the C-C bond rather than the intermediates tautomerization. These calculations rationalize the available experimental observations and can be valuable in optimizing the experimental conditions of asymmetric organic-catalyzed reactions of aldehydes or ketones.展开更多
The molecular structures of indazole and 3-halogeno-indazole tautomers were calculated by the B3LYP method at the 6-311G^＊＊ level, both in the gaseous and aqueous phases, with full geometry optimization. The geometr...The molecular structures of indazole and 3-halogeno-indazole tautomers were calculated by the B3LYP method at the 6-311G^＊＊ level, both in the gaseous and aqueous phases, with full geometry optimization. The geometry and electronic structure of the tautomers of indazole, 3-halogeno-indazole and their transition states were obtained. The Onsager solvate theory model was employed for the aqueous solution calculations. The results of the calculation indicated that the N1-H form of the studied molecule is more stable than that of the N2-H form. The influences of the different 3-halogeno and solvent effects on the geometry, energy, charge and activation energy were discussed. The reaction mechanism of the tautomerization of indazole and 3-halogeno-indazole was also studied and a three-membered cyclic transition state of the tautomer reaction has been obtained.展开更多
Black phosphorus （BP） is a good candidate for studying strain effects on two- dimensional （2D） materials beyond graphene and transition-metal dichalcogenides. This is because of its particular ability to sustain h...Black phosphorus （BP） is a good candidate for studying strain effects on two- dimensional （2D） materials beyond graphene and transition-metal dichalcogenides. This is because of its particular ability to sustain high strain and remarkably anisotropic mechanical properties resulting from its unique puckered structure. We here investigate the dependence of lattice vibrational frequencies on cry- stallographic orientations in uniaxially strained few-layer BP by in-situ strained Raman spectroscopy. The out-of-plane A1 mode is sensitive to uniaxial strain along the near-armchair direction whereas the in-plane B2g and A2 modes are sensitive to strain in the near-zigzag direction. For uniaxial strains applied away from these directions, all three phonon modes are linearly redshifted. Our experimental observation is explained by the anisotropic influence of uniaxial tensile strain on structural properties of BP using density functional theory. This study demonstrates the possibility of selective tuning of in-plane and out-of-plane phonon modes in BP by uniaxial strain and makes strain engineering a promising avenue for extensively modulating the optical and mechanical properties of 2D materials.展开更多
The tautomerization of H2NCH2C(OH)NH to H2NCH2CONH2 is an important step by way of Strecker synthesis for the production of glycine in the interstellar medium (ISM) with respect to the origin of amino acids on the ear...The tautomerization of H2NCH2C(OH)NH to H2NCH2CONH2 is an important step by way of Strecker synthesis for the production of glycine in the interstellar medium (ISM) with respect to the origin of amino acids on the early Earth.Our work indicates two mechanisms for the tautomerization to occur.k CVT/SCT (rate constant) is 45.6s-1 at 50 K,obtained with the small curvature tunneling (SCT) approximation and canonical variational transition state theory (CVT),to support one mechanism assisted by quantum tunneling in the ISM.Another mechanism is through the (H2O) 2-coupled proton transfer.In the (H2O)2 coupled reaction,two H2O molecules act as a catalyst to reduce the barrier energy by 23.7 kcal mol 1,and cooperatively let a proton pass a hydrogen-bonded bridge composed of H2NCH2C(OH)NH with (H2O)2.kTST is 8.08×10-4 s-1 at 100 K,calculated with TST kinetics,to demonstrate the mechanism.Therefore,the tautomerization is feasible in the ISM.H2NCH2C(OH)NH and H2NCH2CONH2 will be detected in the ISM and found in carbonaceous chondrites.The results present new evidence for the third theory on the origin of amino acids on the early Earth.展开更多
文摘The enamines, iminium ions, and oxazolidinones are thought to be the key intermediates in the proline-catalyzed reactions of aldehydes or ketones, but there is an extensive contro- versy about their roles. Here, the corresponding transition states connecting any two of the three kinds of species are located at the wB97XD/6-311＋＋G＊＊ level of theory. The calcula- tions demonstrate that the oxazolidinones are the predominant species in both the gas phase and solvents; there exists tautomeric equilibrium among these species and the equilibriums are controlled by the employed solvents and temperature in the reaction. These results demonstrate that the concentration and role of the mentioned species are controlled by the employed solvent and temperature. A new reaction pathway is presented herein for the trans- formation between iminium ions and oxazolidinones through iminium ion-water complex and oxazolidinone-water complex. The calculations demonstrate that the rate-limiting step in proline-catalyzed Mannich reaction between acetaldehyde/keteones and N-Boc imines is the formation of the C-C bond rather than the intermediates tautomerization. These calculations rationalize the available experimental observations and can be valuable in optimizing the experimental conditions of asymmetric organic-catalyzed reactions of aldehydes or ketones.
文摘The molecular structures of indazole and 3-halogeno-indazole tautomers were calculated by the B3LYP method at the 6-311G^＊＊ level, both in the gaseous and aqueous phases, with full geometry optimization. The geometry and electronic structure of the tautomers of indazole, 3-halogeno-indazole and their transition states were obtained. The Onsager solvate theory model was employed for the aqueous solution calculations. The results of the calculation indicated that the N1-H form of the studied molecule is more stable than that of the N2-H form. The influences of the different 3-halogeno and solvent effects on the geometry, energy, charge and activation energy were discussed. The reaction mechanism of the tautomerization of indazole and 3-halogeno-indazole was also studied and a three-membered cyclic transition state of the tautomer reaction has been obtained.
文摘Black phosphorus （BP） is a good candidate for studying strain effects on two- dimensional （2D） materials beyond graphene and transition-metal dichalcogenides. This is because of its particular ability to sustain high strain and remarkably anisotropic mechanical properties resulting from its unique puckered structure. We here investigate the dependence of lattice vibrational frequencies on cry- stallographic orientations in uniaxially strained few-layer BP by in-situ strained Raman spectroscopy. The out-of-plane A1 mode is sensitive to uniaxial strain along the near-armchair direction whereas the in-plane B2g and A2 modes are sensitive to strain in the near-zigzag direction. For uniaxial strains applied away from these directions, all three phonon modes are linearly redshifted. Our experimental observation is explained by the anisotropic influence of uniaxial tensile strain on structural properties of BP using density functional theory. This study demonstrates the possibility of selective tuning of in-plane and out-of-plane phonon modes in BP by uniaxial strain and makes strain engineering a promising avenue for extensively modulating the optical and mechanical properties of 2D materials.
基金supported by the One-Hundred-Talents Project of Chinese Academy of Sciences,and the Academic Talent Foundation of Yunnan Province,China (Grant No.2006PY01-29)
文摘The tautomerization of H2NCH2C(OH)NH to H2NCH2CONH2 is an important step by way of Strecker synthesis for the production of glycine in the interstellar medium (ISM) with respect to the origin of amino acids on the early Earth.Our work indicates two mechanisms for the tautomerization to occur.k CVT/SCT (rate constant) is 45.6s-1 at 50 K,obtained with the small curvature tunneling (SCT) approximation and canonical variational transition state theory (CVT),to support one mechanism assisted by quantum tunneling in the ISM.Another mechanism is through the (H2O) 2-coupled proton transfer.In the (H2O)2 coupled reaction,two H2O molecules act as a catalyst to reduce the barrier energy by 23.7 kcal mol 1,and cooperatively let a proton pass a hydrogen-bonded bridge composed of H2NCH2C(OH)NH with (H2O)2.kTST is 8.08×10-4 s-1 at 100 K,calculated with TST kinetics,to demonstrate the mechanism.Therefore,the tautomerization is feasible in the ISM.H2NCH2C(OH)NH and H2NCH2CONH2 will be detected in the ISM and found in carbonaceous chondrites.The results present new evidence for the third theory on the origin of amino acids on the early Earth.
