A highly enantioselective palladium-catalyzed intramolecular Heck reaction of unactivated alkenes is developed,which provides a powerful route to access a broad range of chiral 3,3-disubstituted-2,3-dihydrobenzofurans...A highly enantioselective palladium-catalyzed intramolecular Heck reaction of unactivated alkenes is developed,which provides a powerful route to access a broad range of chiral 3,3-disubstituted-2,3-dihydrobenzofurans bearing all-carbon quaternary stereocenter of interest in pharmaceutical research.Its salient features include high yield,excellent chemo-and enantioselectivity,mild conditions,a broad substrate scope as well as versatile transformations of the product.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
1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl pho...1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl phosphine ligands have already been reported,it is still an challenging subject tocreate new ferrocenyl phosphine ligands in order to cover asymmetric reactions in which conventional ligands do not effectively work[1].We happned to discover that 1,5-dilithiation of o-TMS blocked ferrocene 1 pr...展开更多
A new chiral ligand N p toluenesulfonyl 2,2′ dimethoxy 6,6′ diaminobiphenyl (Ts DMBDPPA) was prepared from 2,2′ dimethoxy 6,6′ diaminobiphenyl via N tosylation. Its Ru(II) complex was effec...A new chiral ligand N p toluenesulfonyl 2,2′ dimethoxy 6,6′ diaminobiphenyl (Ts DMBDPPA) was prepared from 2,2′ dimethoxy 6,6′ diaminobiphenyl via N tosylation. Its Ru(II) complex was effective catalysts for catalytic asymmetric transfer hydrogenation of aromatic ketones (with ee 's up to 69.3%).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
报道了手性膦烯配体在金属铑催化的芳基硼酸对β-芳基-α,β-不饱和磺酸酯不对称共轭加成中的应用.经过系统的反应条件筛选和配体结构优化,发现含手性1,1'-联-2-萘酚骨架的膦烯配体L7与Rh(I)形成的催化剂可以高对映选择性地实现β-...报道了手性膦烯配体在金属铑催化的芳基硼酸对β-芳基-α,β-不饱和磺酸酯不对称共轭加成中的应用.经过系统的反应条件筛选和配体结构优化,发现含手性1,1'-联-2-萘酚骨架的膦烯配体L7与Rh(I)形成的催化剂可以高对映选择性地实现β-芳基-α,β-不饱和磺酸酯化合物的不对称1,4-加成反应.此反应体系条件温和,底物普适性广,并取得了较高的收率(up to 95%)和优秀的对映选择性(up to 99%ee),为合成手性偕二芳基取代的磺酸酯类化合物提供了一种新方法.展开更多
基金support of the National Key R&D Program of China(No.2021YFF0701600),NSFC(No.22031004)the Shanghai Municipal Education Commission(No.20212308)China Postdoctoral Science Foundation(No.2022M713667)and STCSM(No.23ZR1445600).
文摘A highly enantioselective palladium-catalyzed intramolecular Heck reaction of unactivated alkenes is developed,which provides a powerful route to access a broad range of chiral 3,3-disubstituted-2,3-dihydrobenzofurans bearing all-carbon quaternary stereocenter of interest in pharmaceutical research.Its salient features include high yield,excellent chemo-and enantioselectivity,mild conditions,a broad substrate scope as well as versatile transformations of the product.
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1 Results The unique structure of chiral ferrocenes allows one to design a variety of chiral phosphine ligands,which are useful tools for metal catalyzed asymmetric reactions.Although some useful chiral ferrocenyl phosphine ligands have already been reported,it is still an challenging subject tocreate new ferrocenyl phosphine ligands in order to cover asymmetric reactions in which conventional ligands do not effectively work[1].We happned to discover that 1,5-dilithiation of o-TMS blocked ferrocene 1 pr...
文摘A new chiral ligand N p toluenesulfonyl 2,2′ dimethoxy 6,6′ diaminobiphenyl (Ts DMBDPPA) was prepared from 2,2′ dimethoxy 6,6′ diaminobiphenyl via N tosylation. Its Ru(II) complex was effective catalysts for catalytic asymmetric transfer hydrogenation of aromatic ketones (with ee 's up to 69.3%).
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.
文摘报道了手性膦烯配体在金属铑催化的芳基硼酸对β-芳基-α,β-不饱和磺酸酯不对称共轭加成中的应用.经过系统的反应条件筛选和配体结构优化,发现含手性1,1'-联-2-萘酚骨架的膦烯配体L7与Rh(I)形成的催化剂可以高对映选择性地实现β-芳基-α,β-不饱和磺酸酯化合物的不对称1,4-加成反应.此反应体系条件温和,底物普适性广,并取得了较高的收率(up to 95%)和优秀的对映选择性(up to 99%ee),为合成手性偕二芳基取代的磺酸酯类化合物提供了一种新方法.
