In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects o...In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.展开更多
The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dp...The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.展开更多
Nucleophilic chiral phosphine catalysis has been prosperous in asymmetric synthesis over the past two decades. Various tunable chiral phosphines display excellent activity and selectivity in asymmetric transformations...Nucleophilic chiral phosphine catalysis has been prosperous in asymmetric synthesis over the past two decades. Various tunable chiral phosphines display excellent activity and selectivity in asymmetric transformations including acycloaddition reactions and cycloaddition reactions. Enantiomerically enriched cyclic compounds are ubiquitous in natural products and drug molecules. These phosphinecatalyzed reactions provide effective and extensive strategies for the synthesis of a series of complex cyclic compounds as well as the synthesis of chiral compounds which could be easily transformed to carbocycles and heterocycles. This minireview summarizes recent developments in this area and highlights meaningful breakthroughs.展开更多
The （COCl）2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and ...The （COCl）2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.展开更多
The catalytic potential of carbon nucleophiles has seldom been disclosed due to their reactivity toward carbon electrophiles to form stable carbon-carbon bonds,which are too strong to be cleaved for the expected catal...The catalytic potential of carbon nucleophiles has seldom been disclosed due to their reactivity toward carbon electrophiles to form stable carbon-carbon bonds,which are too strong to be cleaved for the expected catalytic cycles. We have developed an efficient catalytic cyanosilylation of carbonyl compounds with an in situ generated alkene/phosphine adduct,which is tuned not to couple with a carbonyl compound or an electron-deficient alkene under the reaction conditions when its nucleophilicity is trans-lated into catalytic activity. In the presence of 3 mol% of methyl acrylate and 3 mol% of triphenylphosphine,a broad range of alkyl,alkenyl,and aryl ketones and aldehydes undergo cyanosilylation reaction with trimethylsilyl cyanide at room temperature to yield structurally diversified cyanohydrin silyl ethers in excellent yields. By using methyl acrylate/triphenylphosphine as a highly effective nucleophilic catalyst system for the cyanosilylation of carbonyl compounds,this study demonstrates a new concept for the development of useful organocatalysis utilizing the nucleophilicity of alkene/phosphine adducts generated in situ.展开更多
基金the NSFC(No.20272037),the Doctor's Foundation of Education Ministry of China(No.20030610022)Foundation of Xihua University(No.R0723315) and(No.07ZA109) for the financial support of this work.
文摘In this paper,a series of optically active MeO-BIPHEP-type ligands,（S）-6,6′-dimethoxy-2,2’-bis（di-p-alkoxyphenylphosphine）- 1,1′-biphenyl were synthesized and used to prepare the ruthenium complex.The effects of para-substituted were observed,the results showed that the ruthenium catalysts[diphosphine RuCl;diamine]containing both t-Bu and i-Pr substitutions have better activities and enantioselectivities than the non-substituted ruthenium catalysts in the asymmetric hydrogenation of acetophenone.
基金financially supported by the National Natural Science Foundation of China(Nos.21673077,21473058,and 21273077)
文摘The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.
基金financial support from the National Basic Research Program of China(973 Project,No.2015CB856603)the National Natural Science Foundation of China(Nos.20472096,21372241,21361140350,20672127,21421091,21372250,21121062,21302203,20732008 and 21572052)
文摘Nucleophilic chiral phosphine catalysis has been prosperous in asymmetric synthesis over the past two decades. Various tunable chiral phosphines display excellent activity and selectivity in asymmetric transformations including acycloaddition reactions and cycloaddition reactions. Enantiomerically enriched cyclic compounds are ubiquitous in natural products and drug molecules. These phosphinecatalyzed reactions provide effective and extensive strategies for the synthesis of a series of complex cyclic compounds as well as the synthesis of chiral compounds which could be easily transformed to carbocycles and heterocycles. This minireview summarizes recent developments in this area and highlights meaningful breakthroughs.
基金the Natural Science Foundation of China(Nos.21021001,21072134 and J1103315/J0104)for financial support
文摘The （COCl）2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.
基金supported by the National Natural Science Foundation of China (20732006 and 20672105) and the Chinese Academy of Sciences
文摘The catalytic potential of carbon nucleophiles has seldom been disclosed due to their reactivity toward carbon electrophiles to form stable carbon-carbon bonds,which are too strong to be cleaved for the expected catalytic cycles. We have developed an efficient catalytic cyanosilylation of carbonyl compounds with an in situ generated alkene/phosphine adduct,which is tuned not to couple with a carbonyl compound or an electron-deficient alkene under the reaction conditions when its nucleophilicity is trans-lated into catalytic activity. In the presence of 3 mol% of methyl acrylate and 3 mol% of triphenylphosphine,a broad range of alkyl,alkenyl,and aryl ketones and aldehydes undergo cyanosilylation reaction with trimethylsilyl cyanide at room temperature to yield structurally diversified cyanohydrin silyl ethers in excellent yields. By using methyl acrylate/triphenylphosphine as a highly effective nucleophilic catalyst system for the cyanosilylation of carbonyl compounds,this study demonstrates a new concept for the development of useful organocatalysis utilizing the nucleophilicity of alkene/phosphine adducts generated in situ.
