过渡金属催化下基于醇C-O键活化的C-C交叉偶联反应研究

醇在自然界广泛存在，许多醇也是价廉易得的工业产品。直接利用醇作为原料进行C-C键的构建，是比应用醇的衍生物更为原子和步骤经济的转化反应，对有机合成具有显著的意义。我们拟通过过渡金属催化进行醇的C-O键活化进而实现C-C键构建。拟研究的反应包括 (1) 过渡金属催化的醇与金属有机试剂如Grignard试剂、有机锌试剂、有机硼试剂和有机铝试剂的偶联；(2) 过渡金属催化的醇与原位形成的芳基或杂芳基碳亲核试剂的偶联；(3) 过渡金属催化下经由芳基或杂芳基C-H键活化与醇的偶联。同时对反应机理进行研究。通过该项研究，深入地理解醇的C-O键的催化活化和转化过程，实现苄醇、烯丙醇和普通一级和二级醇与亲核试剂的偶联。也将通过对芳香或杂芳香C-H键和醇的C-O键的催化活化，实现更加原子经济的C-H/C-O偶联。

Alcohols broadly exist in nature and are also cheaply available industrial products. Construction of C-C bonds from alcohols are more atom- and step-economical than that from alcohol derivatives and are of considerable significance in organic synthesis. We intend to study transition-metal-catalyzed C-C bond formation via C-O bond activation of alcohols. The reactions we will study involve: (1) transition-metal-catalyzed cross-coupling of alcohols with organometallic reagents such as Grignard reagents, organozinc reagents, organoboron reagents, and organoaluminum reagents; (2) transition-metal-catalyzed cross-coupling of alcohols with in situ formed (hetero)aryl anions; and (3) transition-metal-catalyzed C-H activation of (hetero)aromatic compounds and cross-coupling with alcohols. The mechanisms of these reactions will also be studied. Through the studies mentioned above, the catalytic activation and tranformation of the C-O bonds of alcohols will be well understood and cross-couplings of alcohols involving allyl alcohols, benzyl alcohols, and normal primary and secondary alcohols with various nucleophiles will be performed. The more atom-economical couplings via catalytic C-H activation of (hetero)aromatic compounds and C-O activation of alcohols will also be revealed.