手性环丙烷骨架配体及其Fe（Ⅲ）、铑(Ⅱ)配合物的设计、合成及在不对称催化中的应用

Chiral cyclopropane-based ligand offers an advantageous combination of structural rigidity, multiple chiral centers and unusual bond angles. The unique structural features of the cyclopropyl moiety in orienting the heteroatoms bound to the metal rander the cyclopropane-based structural classes ligand to be a new star in asymmetric catalysis system. The project is aimed to synthesize two types of new enantiomerically pure cis-chiral cyclopropane skeleton ligands based on the nethodology for the preparation of sily-protected cis-2-aminocyclopropanols developed by applicant. The synthesis of ligands involves deprotection of N-tert-Butanesulfinyl and silicon followed by derivatization of the atoms of nitrogen and oxygen. The synthesized two ligands will be ued to coordinate the iron(III) and rhodium(II), respectively. The ligand prepared by derivatization of cis-2-aminocyclopropanols from methylene pyridyl on atom of nitrogen (or both nitrogen and oxygen) is proposed to chelate with iron(III)（Scheme 14 - 15）. The type of iron(III) - (N, O) complex are expected to show enantioselective in oxidation reaction. The carboxamide ligand bearing chiral cyclopropane skeleton will coordinate with dirhodium （Scheme 17 - 18）, which is potential reactivity and selectivity in the reaction of decomposition diazo compound and the follow-up carbene reactions. The structure of the ligands designed above involved several adjustable points which can influence dramatically the properties of complex such as stability, reactivty, chemoselectity and enantioseletity by inducing variable substituent bearing different electronic and stric effects. Their structure features provide a larger space for the screening the asymmetric reactions matched with the designed complex. Additional, intermediate conformation in the process of reaction is limited due to direct connection to rigid cyclopropane skeleton of coordinated atoms nitrogen and oxygen. The full utilization rigid cyclopropane skeleton caused by direct connection will improve the enantioseletity in asymmetric system, which provide a guarantee for the good result of chiral cyclopropane-based complex in asymmetric catalysis.

手性环丙烷骨架配体由于其刚性结构、多手性中心及非常规键角，与金属配位后形成独特手性环境，是不对称催化领域的新星。项目在申请人发展的构建手性环丙烷骨架氨基醇硅醚方法的基础上，经脱亚磺酰基、脱硅烷基、N，O原子衍生化等步骤，拟合成两类新型光学纯顺式手性环丙烷骨架配体，分别与金属配位用于催化不对称反应：发展N(或N,O)-吡啶甲基化顺式手性环丙烷骨架氨基醇配体与铁配位形成Fe(Ⅲ) -(N, O)配合物（图14-15）用于不对称氧化反应；发展顺式手性环丙烷骨架酰胺铑配合物 (图17-18）催化不对称重氮分解反应。以上配体含多个可调换位点，引入不同取代基可调节配合物稳定性及手性诱导能力，为筛选与配合物相匹配的不对称反应提供较大空间；且配位原子与环丙烷直接相连，能充分利用环丙烷特殊结构限制配体构象，减少中间体构象，提高反应立体选择性，为手性环丙烷骨架配合物在不对称催化中取得优良效果提供保证。

手性环丙烷骨架配体由于其刚性结构、多手性中心及非常规键角，与金属配位后形成独特手性环境，是不对称催化领域的新星。项目在申请人发展的构建手性环丙烷骨架氨基醇硅醚方法的基础上，经脱亚磺酰基、脱硅烷基、N，O原子衍生化等步骤，拟合成两类新型光学纯顺式手性环丙烷骨架配体，分别与金属配位用于催化不对称反应.（1）实现了手性三元环氨基醇配体与Zn（Ⅱ）的配合物催化苯乙炔与酰硅的加成反应，ee值最高93%。.（2）环丙烷骨架的稳定性：由于本项目所涉及环丙烷骨架的氨基醇稳定性较差，如何实现该配体的应用，是本项目的难点。本项目首先合成了稳定的三元环氨基醇配体L1.，旨在催化含三氟甲基的Frield-Crafts反应，该反应的研究正在进行中；