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中文摘要：
现代化学与药物学科的发展对相关的不对称催化与合成化学提出了新的、更高的要求，需要手性控制化学能够达到高度可控的高选择性和高原子利用度（原子经济性）的理想境地。本项目拟将借鉴含金属生物酶催化中多活性中心协同作用机理并在已有研究基础上进行设计制备不同结构的基于手性金属配合物及有机小分子的MFMC催化体系，发展新型组装可控的手性杂多金属体系等多活性中心MFMC催化剂，考察其在不对称氟化与硅烷化反应中的应用研究，建立手性含氟、含硅手性化合物的高效合成途径。基于大量的研究数据凝练提升不对称反应理论与策略，如结合研究数据与理论计算研究MFMC催化体系的构效关系，提出具有一定规律性的实用理论或经验性的概念。以此为依据不断更新设计可应用于多类反应的具有高催化活性和立体选择性的新型手性MFMC催化剂，同时为自组装化学和超分子催化提供可借鉴的方法与策略，为相关手性物质尤其是生物活性物质的合成提供高效合成途径。
英文摘要：
Homogeneous catalysis；asymmetric catalysis；biomimetic catalysis；asymmetric fluorination；catalytic silylation
结论摘要：
现代化学与药物学科的发展对相关的不对称催化与合成化学提出了新的、更高的要求，需要手性控制化学能够达到高度可控的高选择性和高原子利用度（原子经济性）的理想境地。本项目受含金属生物酶催化中多活性中心协同作用机理的启发，在已有研究基础上设计制备了不同结构的手性金属配合物及有机小分子催化剂组合的MFMC 催化体系，在四年的项目执行期里成功发展新型组装可控的手性杂多金属体系等多活性中心MFMC 催化剂，并考察了其在不对称氟化与硅烷化反应中的应用研究，建立了手性含氟、含硅手性化合物的高效合成途径。基于近10种反应的研究数据凝练结合部分理论计算研究，研究了MFMC 催化体系的构效关系，提出了具有一定规律性的发现，为相关手性物质尤其是生物活性物质的合成提供高效合成途径。本项目的主要科学发现包括（1）多手性中心新型配体Ar-BINMOL及其含膦Ar-BINMOL主导的MFMC催化体系研究；（2）Ar-BINMOL衍生的多手性中心Salen或Salan配体控制的金属催化氟硅转化反应研究；（3）BINOL衍生的多功能N,O,P-新型膦配体（该配体命名为HZNU-Phos）主导的MFMC催化体系；（4）可用于MFMC复杂催化体系的新型手性配体的设计与合成；（5）双组分小分子催化剂参与的MFMC复杂催化体系及其他相关氟硅转化反应研究。基于上述工作累计发表学术论文52篇，其中二区以上论文24篇；项目执行期间获得省部级二等奖1项，国际学术奖1项。
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期刊论文
Powerful Amino Acid Derived Bifunctional Phosphine Catalysts Bearing a Hydrogen Bond Donor in Asymme
Catalytic Synthesis of Functional Silicon-Stereogenic Silanes through Candida antarctica Lipase B Ca
Molecular Assembly of an Achiral Phosphine and a Chiral Primary Amine: A Highly Efficient Supramolec
Chiral Ar-BINMOL-derived salan as fluorescent sensor for recognition of CuCl and cascade discriminat
Desymmetrization Catalyzed by Transition-Metal Complexes: Enantioselective Formation of Silicon-Ster
Catalytic Silylations of Alcohols: Turning Simple Protecting-Group Strategies into Powerful Enantios
Enantioselective Copper-Catalyzed Azide-Alkyne Click Cycloaddition to Desymmetrization of Maleimide-
Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C-X Bond Clea
Investigation of the mitsunobu reaction of binol and cinchona alkaloids: inversion or retention of c
Fe-catalyzed cycloaddition of indoles and o-phthalaldehyde for the synthesis of benzo[b]carbazoles w
Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper-Catalyzed Conjugate Addition
ENANTIOSELECTIVE FLUORINATION REACTION OF beta-KETOESTER-CATALYZED CHIRAL PRIMARY AMINE-BASED MULTIF
Enantioselective direct fluorination and chlorination of cyclic beta-ketoesters mediated by phase-tr
Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic
Synthesis of Ar-BINMOL Ligands by [1,2]-Wittig Rearrangement to Probe Their Catalytic Activity in 1,
Probing the evolution of an Ar-BINMOL-derived salen-Co(III) complex for asymmetric Henry reactions o
Dehydrogenation and oxidative coupling of alcohol and amines catalyzed by organosilicon-supported Ti
Enantioselective Primary Amine Catalyzed Aldol-Type Construction of Trifluoromethylated Tertiary Alc
Modular Synthesis of Ar-BINMOL-Phos for Catalytic Asymmetric Alkynylation of Aromatic Aldehydes with
Enantioselective Fluorination of beta-Ketoamides Catalyzed by Ar-BINMOL-derived Salan-Copper Complex
Aromatic-Amide-Derived Nonbiaryl Atropisomer as Highly Efficient Ligand for Asymmetric Silver-Cataly
Silylations of Arenes with Hydrosilanes: From Transition-Metal-Catalyzed CX Bond Cleavage to Environ
Enantioselective conjugate addition of cyanide to chalcones catalyzed by a magnesium-Py-BINMOL compl
Construction of an all-substituted pyrrolidine derivative with multiple stereogenic centers and Bett
Base-promoted [1,4]-Wittig rearrangement of chalcone-derived allylic ethers leading to aromatic beta
DMSO as oxidant and sulfenylating agent for metal-free oxidation and methylthiolation of alcohol-con
Modulation of Silver-Titania Nanoparticles on Polymethylhydrosiloxane-based Semi-Interpenetrating Ne
Development of a Novel Multifunctional N,P Ligand for Highly Enantioselective Palladium-Catalyzed As
Efficient Palladium-Catalyzed CO Hydrogenolysis of Benzylic Alcohols and Aromatic Ketones with Polym
Aromatic Amide-Derived Non-Biaryl Atropisomers as Highly Efficient Ligands in Silver-Catalyzed Asymm
Nanosilver as a new generation of silver catalysts in organic transformations for efficient synthesi
Malononitrile-Assisted Highly Chemoselective Bismuth Triflate Catalyzed Conjugate Reduction of alpha
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