有机三明治排列的多面3D手性

Chirality exists ubiquitously in the functional molecules and higher structures of plants and animals in nature.Chirality has attracted much attention in science and technology community because of its importance and special status in chemistry, biology, medicine and materials. Chirality documented in the literature is generally divided into center chirality, axial chirality, helical chirality and double-sided chirality.The applicant's research group has recently discovered a conceptually new chirality: multi-layer 3D chirality. This new chirality is characterized by sandwich-type of arrangement: it is composed of three almost parallel layers, with the middle layer as the central layer, one of which is at the top and the other at the bottom of the central plane. The upper and lower surfaces are mutually dependent and restricted to avoid possible isomerization of mirror isomers.This project is planned to investigate the design, synthesis and applications of novel 3D chiral molecules in asymmetric synthesis and catalysis, so as to lay a new molecular foundation for the precise construction of chiral drugs and functional materials.The specifictopics in this proposal include : (1) Brønstedand Lewis acid catalystsanchored bymulti-layer 3D chiral chemistry; (2) recycled and reusable multi-layer 3D chiral MacMillan catalyst and applications to various reactions; (3) chiral phosphorus ligands and its use for asymmetric catalytic reactions via unpresentedasymmetric environment; (4) new methodology for formingmulti-layer 3D chiral compounds catalyzed by multi-layer 3D ligands; (5) asymmetric reactions controlled by multifaceted 3D catalysts including asymmetric hydrogenation of GAP-imine and enamine substrates, asymmetric Morita-Baylis-Hillman reactions, asymmetric Friedel-Crafts and Diels-Alder reactions.

手性因其在化学，生物，医学和材料中的重要性和特殊地位，受到广泛关注。手性分为中心/轴/螺旋/双面手性。申请人课题组发现了多面3D手性。该手性具有三明治排列特征：中间层的上方和下方各一层，上下两个层面是相互依存/制约，以避免镜像异构体异构化。本项目将研究多面3D手性分子的设计，合成和其在不对称催化中的应用。研究方向分为：（1）多面3D手性中的布朗斯特酸和路易斯催化剂；（2）可回收重复使用的多面3D手性的MacMillan催化剂和应用；（3）全新手性环境下的手性磷配体和不对称催化反应；（4）通过多面3D配体催化合成多面3D手性化合物。（5）多面3D催化剂控制的反应包括，GAP-imine和enamine为底物的不对称氢化，Morita-Baylis-Hillman反应，Friedel-Crafts反应和Diels-Alder反应。

手性现象在地球孕育生命之初就存在于自然界中，存在于微观生物(如螺旋状细菌)到宏观物体(如海贝壳)之中。像多肽/蛋白质、DNA/RNA和碳水化合物等功能性生物分子都包含几种手性构型。现代药物越来越依赖通过手性来控制其高效性和选择性，用以减少剂量和不必要副作用。在现代材料科学中，为了实现具有挑战性的光电特性，也需要对手性进行控制。在过去的几十年里，虽然在控制手性方面已经取得了很大的进展，但几乎没有关于新手性的研究报道。 本项目建立了多面柔性折叠手性和向标手性。前者不同于刚性螺烯（螺旋型），而是折叠型。后者区别于传统旋转手性，不只有三个主要能垒，而是六个能垒。另外，多面柔性折叠手性可以应用于高分子。本项目建立了聚集诱导合成（AIS）、不对称合成（AIAS）、聚集诱导催化（AIC）和不对称催化（AIAC）概念。己知控制手性方法有不对称手性辅基、手性试剂、手性溶剂以及手性催化剂，而通过调节聚集诱导控制产出手性相反产物，是第五种控制手性方法，此方法也是介于均相催化和固相催化之间的第三种催化。聚集诱导旋光也是一个新概念。与手性发光不同的是旋光参数可以是单一波长的激光，而且强度和波长可调，因为光源是原子光谱而来。该项目的研究成果可望在化学、物理学、生物学、农药、制药和医学以及材料科学方面产生影响。新手性的潜在应用包括但不限于手性配体/催化剂、新型氨基酸/多肽、用于捕光的纳米材料、生物混合系统、手性传感器、自旋选择性激子输运、光学领域芯片级光学元件、量子信息和存储。