C-C bond activation has emerged as a powerful tool for the construction of complex molecules.Herein,we report a dual ligands relay-promoted transformation of unstrained aryl,alkenyl and alkynyl ketones to the correspo...C-C bond activation has emerged as a powerful tool for the construction of complex molecules.Herein,we report a dual ligands relay-promoted transformation of unstrained aryl,alkenyl and alkynyl ketones to the corresponding polyfluoroarenes and nitriles via C-C(=O)bond cleavage and subsequent decarboxylative arylation process.Various polyfluoroarene and nitrile products are obtained in one pot under cyanide-free conditions.The protocol features high atom economy,broad functional group tolerance and excellent heterocyclic compatibility.The late-stage functionalization of the drug and natural product demonstrated the synthetic utility of our protocol.Furthermore,the decisive role of the dual ligands was clarified and the mechanistic rationale including theβ-C elimination as the rate-limiting step was supported by detailed density functional theory(DFT)studies.展开更多
InAlN/GaN heterostructures were grown on sapphire substrates by low-pressure metal organic chemical vapor deposition. The influences of NH3 flux and growth temperature on the In composition and morphologies of the lnA...InAlN/GaN heterostructures were grown on sapphire substrates by low-pressure metal organic chemical vapor deposition. The influences of NH3 flux and growth temperature on the In composition and morphologies of the lnAlN were investigated by X-ray diffraction and atomic force microscopy. It's found that the In composition increases quickly with NH3 flux decrease. But it's not sensitive to NH3 flux under higher flux. This suggests that lower NH3 flux induces a higher growth rate and an enhanced In incorporation. The In composition also increases with the growth temperatures decreasing, and the defects of the InAlN have close relation with In composition. Unstrained lnAlN with In composition of 17% is obtained at NH3 flux of 500 sccm and growth temperature of 790 ℃. The InAlN/GaN heterostructure high electron mobility transistor sample showed a high two-dimensional electron gas (2DEG) mobility of 1210 cm2/(V.s) with the sheet density of 2.3 × 10^13 cm^-2 at room temperature.展开更多
C(CO)–alkyl bonds are ubiquitous in a variety of organic molecules,and their selective activation and functionalization are important for the reconstruction of simple ketones into valuable building blocks.However,due...C(CO)–alkyl bonds are ubiquitous in a variety of organic molecules,and their selective activation and functionalization are important for the reconstruction of simple ketones into valuable building blocks.However,due to the thermodynamic and kinetic stability,the cleavage and transformation of the unstrained C(CO)–alkyl bonds remain a significant challenge.Herein,we report a novel silver-catalyzed scission of the unstrained C(CO)–alkyl bond of ketones by reacting with N-isocyanoiminotriphenylphosphorane(NIITP)under mild conditions.This method could transform a variety of unstrained ketones into iminophosphoranes and nitriles in high yields.Experimental and computational studies disclosed the reaction proceeded through an unprecedented[3+2]/retro-[3+2]cycloaddition mechanism.展开更多
基金supported by the Shanghai Institute of Materia Medica,the Chinese Academy of ScienceseNational Natural Science Foundation of China(21772211,21920102003)+4 种基金the Institutes for Drug Discovery and Development,Chinese Academy of Sciences(CASIMM0120163006)the Science and Technology Commission of Shanghai Municipality(17JC1405000,18431907100)the Program of Shanghai Academic Research Leader(19XD1424600)the National Science&Technology Major Project“Key New Drug Creation and Manufacturing Program”,China(2018ZX09711002-006)the China Postdoctoral Science Foundation(2019M662854)
文摘C-C bond activation has emerged as a powerful tool for the construction of complex molecules.Herein,we report a dual ligands relay-promoted transformation of unstrained aryl,alkenyl and alkynyl ketones to the corresponding polyfluoroarenes and nitriles via C-C(=O)bond cleavage and subsequent decarboxylative arylation process.Various polyfluoroarene and nitrile products are obtained in one pot under cyanide-free conditions.The protocol features high atom economy,broad functional group tolerance and excellent heterocyclic compatibility.The late-stage functionalization of the drug and natural product demonstrated the synthetic utility of our protocol.Furthermore,the decisive role of the dual ligands was clarified and the mechanistic rationale including theβ-C elimination as the rate-limiting step was supported by detailed density functional theory(DFT)studies.
基金supported by the National Natural Science Foundation of China(No.61306113)
文摘InAlN/GaN heterostructures were grown on sapphire substrates by low-pressure metal organic chemical vapor deposition. The influences of NH3 flux and growth temperature on the In composition and morphologies of the lnAlN were investigated by X-ray diffraction and atomic force microscopy. It's found that the In composition increases quickly with NH3 flux decrease. But it's not sensitive to NH3 flux under higher flux. This suggests that lower NH3 flux induces a higher growth rate and an enhanced In incorporation. The In composition also increases with the growth temperatures decreasing, and the defects of the InAlN have close relation with In composition. Unstrained lnAlN with In composition of 17% is obtained at NH3 flux of 500 sccm and growth temperature of 790 ℃. The InAlN/GaN heterostructure high electron mobility transistor sample showed a high two-dimensional electron gas (2DEG) mobility of 1210 cm2/(V.s) with the sheet density of 2.3 × 10^13 cm^-2 at room temperature.
基金provided by the National Natural Science Foundation of China(21871043,21961130376)Department of Science and Technology of Jilin Province(20180101185JC,20190701012GH,20200801065GH)the Fundamental Research Funds for the Central Universities(2412019ZD001,2412019FZ006)。
文摘C(CO)–alkyl bonds are ubiquitous in a variety of organic molecules,and their selective activation and functionalization are important for the reconstruction of simple ketones into valuable building blocks.However,due to the thermodynamic and kinetic stability,the cleavage and transformation of the unstrained C(CO)–alkyl bonds remain a significant challenge.Herein,we report a novel silver-catalyzed scission of the unstrained C(CO)–alkyl bond of ketones by reacting with N-isocyanoiminotriphenylphosphorane(NIITP)under mild conditions.This method could transform a variety of unstrained ketones into iminophosphoranes and nitriles in high yields.Experimental and computational studies disclosed the reaction proceeded through an unprecedented[3+2]/retro-[3+2]cycloaddition mechanism.