手性卟啉光催化剂的设计合成及其在可见光催化的不对称反应中的应用

Sunlight is considered an inexpensive, abundant, and environmentally benign form of inexhaustible energy source. Interfacing visible light activated photochemistry with asymmetric catalysis provides new opportunities for the development of synthetic methods for the efficient and green synthesis of chiral molecules and became one of the fastest growing fields in organic chemistry in the last several years. In contrast to a large variety of methods have been developed for the synthesis of chiral compounds by enantioselective catalytic transformations, the research of visible light catalytic asymmetric synthesis still has been hidden in the dark. Moreover, most of asymmetric photochemical reactions we known are typically accomplished by dual catalyst systems: an achiral photocatalyst is frequently combined with a conventional chiral catalyst. Several recent reports demonstrate that they can also be effectively executed by single catalysts, but some intrinsic factors make them difficult to approach the catalysis of a photochemical reaction in a conventional fashion with broad substrate spectrum and high enantioselectivity. Thus, developing a new type of chiral photocatalyst induced by visible light would be scientific significance and particularly valuable. This project focuses on the development of a new type of chiral photocatalyst by using the unique photoelectric conversion characteristics of porphyrin, as well as introducing appropriate chiral building blocks to a porphyrin synthon at meso-position to control the enantioselectivity. We expected to develop a new type of green, efficient, recyclable chiral porphyrin photocatalyst and their application in visible light induced asymmetric synthesis.

太阳光是一种绿色清洁、廉价易得可再生的自然能源。可见光催化的不对称反应为合成手性化合物提供了一个新颖的、符合绿色化学要求的途径，是当前的研究热点。相对于发展比较成熟的一般的不对称催化反应，可见光的不对称催化反应的研究尚处在发展的初期。目前大部分已报道的催化体系仍是将可见光催化剂和其他手性催化剂进行组合使用来实现可见光的不对称催化反应；为数不多的手性光催化剂存在着光电效率不高、反应类型以及反应底物的普适性较少等问题。所以发展一类具有广泛的底物普适性，能够适用于各种类型反应的手性可见光催化剂具有重要的科学意义和应用价值。本项目着重利用卟啉类分子独特的光电转化特性，吸收可见光活化底物；并利用在卟啉环的中位两侧引入手性支链来构建手性环境，高效的实现可见光催化的不对称反应。通过本项目的研究，有望发展出一类绿色、高效、可回收利用的新型手性卟啉光催化剂并将它们广泛的应用到可见光催化的不对称合成中。

太阳光是一种绿色清洁、廉价易得可再生的自然能源。可见光催化的不对称反应为合成手性化合物提供了一个新颖的、符合绿色化学要求的途径，是当前的研究热点。在的研究中，我们成功实现在无光敏剂的条件下，可见光促进的自由基加成反应，构建重要的C-N键以及喹唑啉酮类化合物及其衍生物的合成；揭示该系列催化转化的作用机理，为今后的工作打下了基础。同时，我们还开展了利用电化学方法产生自由基的绿色合成方法学的研究，实现了电催化条件下的P-O键和P-S键的高效构建以及吲哚2,3位的官能团化，并利用流动电化学实验装置实现了10g级别的合成。总体来说，在我们调整了研究计划后我们很好的实现了调整后的研究目标，发表SCI论文6篇和申请发明专利1项，并且培养了2名硕士研究生，十余名本科生。