过渡金属与有机小分子共催化的新型碳-氢官能化反应

In this project, the C-H functionalizations of common tertiary or secondary amines, ethers, allylic or benzylic compounds and other substrates bearing active or inactive sp3 C-H bonds, heteroaryl, aryl coumpounds, and other substrates bearing sp2 C-H bonds，or the substrates bearing sp1 C-H bonds under coorperative transition-metal catalysis and organocatalysis are going to be investigated. Furthermore, their asymmetric reactions will be studied. By relay transition-metal catalysis and organocatalysis, the sp3, sp2, sp1 C-H functionalizations of above compounds are going to be investigated as well. Some of successful catalytic reactions above will be applied into the synthesis of natural products and drugs. The coorperative transition-metal catalysis and organocatalysis can play the roles which a transition-metal catalysis or an organocatalysis can not play alone. The relay transition-metal catalysis and organocatalysis can decrease the reaction steps and isolations, reducing resource consumptions. The C-H functionalization can avoid extra steps for the prefunctionalization of substrates, decreasing environmental pollutions.

本项目研究在过渡金属与有机小分子协同催化下，普通叔胺、普通仲胺、醚、烯丙基化合物、苄基化合物等含活性的α-sp3碳-氢键以及含非活性sp3碳-氢键化合物的碳-氢官能化反应，研究杂芳环、芳环化合物等含sp2碳-氢键和含sp1碳-氢键化合物的的碳-氢官能化反应，进一步开发它们的不对称催化反应。同时，研究在过渡金属与有机小分子替续催化下，上述各种化合物的sp3、sp2、sp1碳-氢键官能化反应及其不对称催化反应。并将一些新催化反应运用到天然产物和药物合成中。利用过渡金属和有机小分子协同催化，能发挥单一催化方式所不能达到的作用；利用过渡金属和有机小分子替续催化，可减少每步反应和分离带来对资源的消耗和对环境的污染；所发生的碳-氢键官能化反应，可避免预官能化等额外的反应和分离步骤, 充分体现绿色化学的特征。

研究出过渡金属和有机小分子共催化的α,β-不饱和酮与烯丙基醋酸酯的MBH反应、过渡金属与布朗斯特酸协同催化下甲基喹啉与甘氨酸酯的脱氢交叉偶联反应、烯丙基α-碳-氢键与醛酮的α-碳-氢键之间的脱氢交叉偶联催化反应、包含Heck反应的多米诺三重催化反应、N-芳基甘氨酸酯与酚的脱氢交叉偶联催化反应和四组分碳-氢官能化/环化/亲核取代串联反应等十多个新型碳-氢官能化催化反应。这些合成反应具有原料简便易得、条件温和、高效和对环境友好等优点；这些合成方法有望应用于一些天然产物和药物分子合成中。部分创新性成果在Org. Lett.、 Eur. J. Chem.、 J.Org. Chem.等著名刊物发表论文18篇，授权专利7项。