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
The chemo-,regio-,and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge.In this study,a Pd-catalyzed hydrofunctionalization is developed fo...The chemo-,regio-,and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge.In this study,a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes.Notably,this methodology is suitable for both phosphine oxide and phosphinate nucleophiles,providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.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
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
The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, ...The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, most ofthe reported methodologies required noble transition-metals. Herein we reported the first highly asymmetricstereoselective synthesis of cyclopentanes bearing chiral quaternary carbon stereocenters of trisubstituted allylicsiloxanes by reductive cyclization of all carbon 1,6-alkynones with the non-noble nickel catalysis of Ni(cod)2 withP-chiral monophosphine ligand (S)-BIDIME. Various multi-substituted functionalized cyclopentanes were obtained in high yields (up to 96%), excellent enantioselectivities (up to >99% ee) and perfect stereoselectivities(>99:1 E/Z). Thirty-two examples were successfully established for this method. Clarified mechanism studieswere investigated first time by React-IR and DFT calculations to understand and explain the ligand-control ofexcellent enantio-stereoselectivity. Gram-scale reaction and control experiments were carried out. A new reactiondesign was proposed for further application of this type of catalysis.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the National Natural Science Foundation of China(NSFC,No.22271241),Yunnan Key Laboratory of Chiral Functional Substance Research and Application(No.202402AN360010)Research Grants Council of Hong Kong(GRF,No.12303422)HKBU KRPS grant for financial support.
文摘The chemo-,regio-,and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge.In this study,a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes.Notably,this methodology is suitable for both phosphine oxide and phosphinate nucleophiles,providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
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%.
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financial support provided by the National Natural Science Foundation of China(No.22061032)Natural Science Foundation of Inner Mongolia(Nos.2020MS02022,and 2022QN02005)+5 种基金Science and Technology Program of Inner Mongolia(No.2020GG0134)Opening-fund from State Key Laboratory of Bio-organic and Natural Products Chemistry of SIOC(No.21300-5206002)“JUN-MA”Highlevel Talents Program of Inner Mongolia University(No.21300-5185121)“Grassland Talents”Program of Inner Mongolia(No.12000-12102414)High-level Recruit Program of Inner Mongolia(No.12000-13000603)Key Project at Central Government Level:the ability establishment of sustainable use for valuable Chinese medicine resources(No.2060302)is sincerely acknowledged。
文摘The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, most ofthe reported methodologies required noble transition-metals. Herein we reported the first highly asymmetricstereoselective synthesis of cyclopentanes bearing chiral quaternary carbon stereocenters of trisubstituted allylicsiloxanes by reductive cyclization of all carbon 1,6-alkynones with the non-noble nickel catalysis of Ni(cod)2 withP-chiral monophosphine ligand (S)-BIDIME. Various multi-substituted functionalized cyclopentanes were obtained in high yields (up to 96%), excellent enantioselectivities (up to >99% ee) and perfect stereoselectivities(>99:1 E/Z). Thirty-two examples were successfully established for this method. Clarified mechanism studieswere investigated first time by React-IR and DFT calculations to understand and explain the ligand-control ofexcellent enantio-stereoselectivity. Gram-scale reaction and control experiments were carried out. A new reactiondesign was proposed for further application of this type of catalysis.
