A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates(HP(S)ROR')toα,β-unsaturated thioamides is disclosed,which constructs vicinal P-chiral and C-chiral centers in generally high diastereoand e...A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates(HP(S)ROR')toα,β-unsaturated thioamides is disclosed,which constructs vicinal P-chiral and C-chiral centers in generally high diastereoand enantioselectivities.In this reaction,the kinetic resolution of HP(S)ROR'occurs,which affords(R)-HP(S)Ph OMe in high enantioselectivity in the addition with(R,R)-Ph-BPE as the ligand.It is found through control experiment that dual“soft-soft”interaction,indicated by both1H and31P NMR experiments,is indispensable in the present reaction.The first“soft-soft”interaction between copper(Ⅰ)catalyst and HP(S)ROR'enables facile deprotonation to generate nucleophilic[Cu]-SPROR'species.The second one between the[Cu]-SPROR'species andα,β-unsaturated thioamides facilitated the nucleophilic addition.Finally,both Michael adducts and(R)-HP(S)PhOMe are easily converted to synthetically useful compounds.展开更多
P-Chiral phosphines and sec-phosphine oxides(SPO) are found in a diverse range of compounds that play crucial roles in various fields, including asymmetric catalysis, materials, agrochemistry, and pharmaceutical chemi...P-Chiral phosphines and sec-phosphine oxides(SPO) are found in a diverse range of compounds that play crucial roles in various fields, including asymmetric catalysis, materials, agrochemistry, and pharmaceutical chemistry. Herein, we describe an enantioselective Ni-catalyzed kinetic resolution of racemic sec-phosphine oxides to obtain the corresponding optically pure Pchiral phosphine oxides and sec-phosphine oxides, respectively. These products are versatile chiral phosphine building blocks that can be used to construct an extensive range of P-chiral phosphines.展开更多
A series of structurally novel P-chiral biaryl bisphosphorus ligands L1-L5 （BABIBOPs） are developed, providing high efficiency for the first time in palladium-catalyzed asymmetric hydrogenation of β-aryl and β-alk...A series of structurally novel P-chiral biaryl bisphosphorus ligands L1-L5 （BABIBOPs） are developed, providing high efficiency for the first time in palladium-catalyzed asymmetric hydrogenation of β-aryl and β-alkyl substituted β-keto esters. With the Pd-1.3 （iPr-BABIBOP） catalyst, a series of chiral β-hydroxyl carboxylic esters are formed in excellent enantioselectivities （up to 〉 99% ee） and yields at catalyst loading as low as 0.01 mol%.展开更多
本文利用低温扫描隧道显微镜(low temperature scanning tunneling microscopy,LT-STM)研究了四联苯分子在半金属Bi(111)表面上的超分子手性及其自组装结构。在极低的覆盖度下,四联苯分子形成纳米尺度的分子团簇,团簇中的分子有平躺和...本文利用低温扫描隧道显微镜(low temperature scanning tunneling microscopy,LT-STM)研究了四联苯分子在半金属Bi(111)表面上的超分子手性及其自组装结构。在极低的覆盖度下,四联苯分子形成纳米尺度的分子团簇,团簇中的分子有平躺和侧躺的取向。随着覆盖度的增加,四联苯分子形成多畴的自组装单层结构。自组装单层的基本结构单元是由两个平躺分子和一个侧躺分子构成的三聚体。高分辩的STM图表明,平躺的四联苯分子表现出结构对称性,而侧躺的四联苯分子表现为四个之字形的突起,表明四个苯环之间发生了扭曲,使得三聚体团簇具有超分子手性。有趣的是,在畴区内部相邻两个三聚体的手性相反;在畴界两侧两个三聚体的手性相同,表明同手性的三聚体之间存在空间位阻作用。当覆盖度增加到一个满层,畴界不复存在,整个分子单层形成长程有序的消旋结构。此外,由于分子与半金属衬底之间较弱的相互作用,无论是侧躺的分子还是平躺的分子,都会受到针尖电场的影响发生移动或转动。上述研究结果为理解四联苯分子和半金属之间的相互作用,超分子手性和分子自组装结构之间的关联,以及制备长程有序的界面结构提供了重要信息。展开更多
Chiral S,P-donor ferrocene-derived ligands were synthesized and applied in the asymmetric hydrogenation of quinolines using the [Ir(COD)Cl]2/S,P-ligand c omplex a s the catalyst in the presence of iodine. The effects ...Chiral S,P-donor ferrocene-derived ligands were synthesized and applied in the asymmetric hydrogenation of quinolines using the [Ir(COD)Cl]2/S,P-ligand c omplex a s the catalyst in the presence of iodine. The effects of the solvent and hydroge n pressure on conversion and enantioselectivity were examined, and up to 82% ee was obtained. The planar chirality plays an important role in this reaction. R- and S-enantiomers of 1,2,3,4-tetrahydroquinoline derivatives were ob tained using ligands 3 and 5, respectively.展开更多
基金the financial support from the National Natural Science Foundation of China(No.22271302)the Science and Technology Commission of Shanghai Municipality(Nos.20JC1417100 and 21XD1424800)+1 种基金CAS Key Laboratory of Synthetic Chemistry of Natural SubstancesShanghai Institute of Organic Chemistry。
文摘A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates(HP(S)ROR')toα,β-unsaturated thioamides is disclosed,which constructs vicinal P-chiral and C-chiral centers in generally high diastereoand enantioselectivities.In this reaction,the kinetic resolution of HP(S)ROR'occurs,which affords(R)-HP(S)Ph OMe in high enantioselectivity in the addition with(R,R)-Ph-BPE as the ligand.It is found through control experiment that dual“soft-soft”interaction,indicated by both1H and31P NMR experiments,is indispensable in the present reaction.The first“soft-soft”interaction between copper(Ⅰ)catalyst and HP(S)ROR'enables facile deprotonation to generate nucleophilic[Cu]-SPROR'species.The second one between the[Cu]-SPROR'species andα,β-unsaturated thioamides facilitated the nucleophilic addition.Finally,both Michael adducts and(R)-HP(S)PhOMe are easily converted to synthetically useful compounds.
基金supported by the National Natural Science Foundaiton of China (22171119)Gansu Province Science and Technology Plan for major projects (21ZD4WA021)key research plan (21YF5WA114)。
文摘P-Chiral phosphines and sec-phosphine oxides(SPO) are found in a diverse range of compounds that play crucial roles in various fields, including asymmetric catalysis, materials, agrochemistry, and pharmaceutical chemistry. Herein, we describe an enantioselective Ni-catalyzed kinetic resolution of racemic sec-phosphine oxides to obtain the corresponding optically pure Pchiral phosphine oxides and sec-phosphine oxides, respectively. These products are versatile chiral phosphine building blocks that can be used to construct an extensive range of P-chiral phosphines.
基金The work is supported by the Strategic Priority Research Program of the Chinese Academy of Sciences （No. XDB20000000）, CAS （QYZDY-SSW-SLH029）, the National Natural Science Foundation of China （Nos. 21432007, 21572246, 21725205） and K C. Wong Education Foundation.
文摘A series of structurally novel P-chiral biaryl bisphosphorus ligands L1-L5 （BABIBOPs） are developed, providing high efficiency for the first time in palladium-catalyzed asymmetric hydrogenation of β-aryl and β-alkyl substituted β-keto esters. With the Pd-1.3 （iPr-BABIBOP） catalyst, a series of chiral β-hydroxyl carboxylic esters are formed in excellent enantioselectivities （up to 〉 99% ee） and yields at catalyst loading as low as 0.01 mol%.
文摘本文利用低温扫描隧道显微镜(low temperature scanning tunneling microscopy,LT-STM)研究了四联苯分子在半金属Bi(111)表面上的超分子手性及其自组装结构。在极低的覆盖度下,四联苯分子形成纳米尺度的分子团簇,团簇中的分子有平躺和侧躺的取向。随着覆盖度的增加,四联苯分子形成多畴的自组装单层结构。自组装单层的基本结构单元是由两个平躺分子和一个侧躺分子构成的三聚体。高分辩的STM图表明,平躺的四联苯分子表现出结构对称性,而侧躺的四联苯分子表现为四个之字形的突起,表明四个苯环之间发生了扭曲,使得三聚体团簇具有超分子手性。有趣的是,在畴区内部相邻两个三聚体的手性相反;在畴界两侧两个三聚体的手性相同,表明同手性的三聚体之间存在空间位阻作用。当覆盖度增加到一个满层,畴界不复存在,整个分子单层形成长程有序的消旋结构。此外,由于分子与半金属衬底之间较弱的相互作用,无论是侧躺的分子还是平躺的分子,都会受到针尖电场的影响发生移动或转动。上述研究结果为理解四联苯分子和半金属之间的相互作用,超分子手性和分子自组装结构之间的关联,以及制备长程有序的界面结构提供了重要信息。
文摘Chiral S,P-donor ferrocene-derived ligands were synthesized and applied in the asymmetric hydrogenation of quinolines using the [Ir(COD)Cl]2/S,P-ligand c omplex a s the catalyst in the presence of iodine. The effects of the solvent and hydroge n pressure on conversion and enantioselectivity were examined, and up to 82% ee was obtained. The planar chirality plays an important role in this reaction. R- and S-enantiomers of 1,2,3,4-tetrahydroquinoline derivatives were ob tained using ligands 3 and 5, respectively.
