碳材料表面恶唑硼烷化及其光催化1,2-二苯基乙二醇不对称合成的研究

1, 2 - diphenyl ethylene glycol has generated an interest amongst scientists because of its important application of chiral synthesis, which is prepared by C-C coupling of benzaldehyde using metal complexes as catalysts. However, most of them existed serious residual in use process and required tough preparation conditions. Therefore, more efficient green catalysts need to be developed. Recently, 1, 2 - diphenyl ethylene glycol was synthesized by applicants under light irradiation, which was catalyzed by metal-free carbon materials (expanded graphite, carbon nanotubes, nano carbon ball, graphene), the process was simple and clean, but it is difficult to control the chiral of the product, Based on these results, we will design and synthesize carbon materials functionalized in situ by oxazole boron alkylation in order to achieve the photocatalytic control of the chiral configuration of 1, 2-diphenyl glycol. Oxazaborolidine provides a stable chiral active sites for the product and carbon materials act as light absorptions sites. The chiral configuration generated in chiral active sites is qucikly transformed by accurate control for wavelengths of light and the conversion of randomly generated chiral configuration is inhibited, so as to achieve the aim of control chiral of products. The research project has opened up a new photocatalytic route, in which non-metallic materials act as a catalyst to achieve control of chiral selectivity. This has a positive significance in green catalysis and sustainable development.

1,2-二苯基乙二醇因其在手性合成中的重要应用一直以来备受关注，目前主要依靠金属配合物催化剂催化苯甲醛C-C耦合来合成，但是相关催化剂存在制备条件苛刻且使用过程中容易残留等问题，因此，需要开发更加高效绿色的催化剂。申请人近期采用来源广泛的非金属碳材料（碳纳米管、膨胀石墨、纳米碳球、石墨烯）在光照条件下合成了1,2-二苯基乙二醇，过程简单、清洁，但产物手性难以控制。基于此成果，本项目首次提出设计合成恶唑硼烷化的碳材料，实现光催化控制1,2-二苯基乙二醇手性构型的思路。碳材料表面原位生成的恶唑硼烷为产物的手性构型的生成提供了稳定的手性活性位；碳材料则作为吸光位，通过精确控制光波长使手性位点控制的手性构型快速转化，并抑制随机生成手性构型的转化，从而达到控制产物手性的目的。本项目的研究开辟了以非金属材料为催化剂实现光催化手性选择性控制的新路线，对实现绿色催化可持续发展具有积极的意义。

1,2-二苯基乙二醇因其在手性合成中的重要应用一直以来备受关注，目前主要依靠金属配合物催化剂催化苯甲醛C-C耦合来合成，但是相关催化剂存在制备条件苛刻且使用过程中容易残留等问题,本项目采用来源广泛的非金属碳材料（碳纳米管、膨胀石墨、纳米碳球、石墨烯）对其表面进行恶唑硼烷化，碳材料表面原位生成的恶唑硼烷为产物的手性构型的生成提供了稳定的手性活性位；碳材料则作为吸光位，在光照条件下表面恶唑硼烷化碳材料催化苯甲醛生成S,S-1,2-二苯基乙二醇，对映体选择性大于95%，过程简单、清洁。本项目的研究开辟了以非金属材料为催化剂实现光催化手性选择性控制的新路线，对实现绿色催化可持续发展具有积极的意义。