过渡金属催化的经由非活化氯代烷烃sp3 C-Cl键断裂的Domino反应研究

项目名称： 过渡金属催化的经由非活化氯代烷烃sp3 C-Cl键断裂的Domino反应研究

项目编号： No.21272232

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 余正坤

作者单位： 中国科学院大连化学物理研究所

项目金额： 80万元

中文摘要： 卤代烃参与的交叉偶联反应是形成C-C键的重要方法，碘代烃和溴代烃以及活化的氯代烃已广泛地作为偶联剂使用。由于非活化氯代烷烃的sp3 C-Cl键难以被活化断裂进行转化，因此非活化氯代烷烃偶联反应在有机合成中的应用受到了很大限制，相关研究极具挑战性。为了突破这种局限性，本申请课题拟利用经由beta或gamma-羰基等基团导向断裂非活化氯代烷烃sp3 C-Cl键形成相对活泼的反应中间体如alpha,beta-不饱和酮（烯酮）和环丙基酮等的Domino反应策略，研究在相对温和条件下过渡金属催化的交叉偶联等反应来构建新的碳-碳与碳-杂原子键，探索相关反应机理与规律，由此发展过渡金属催化的经由非活化氯代烷烃sp3 C-Cl键断裂形成C-C和C-X(X = B，N，O，S)键的有机合成新方法学。开展非活化氯代烷烃的高效转化研究，将有利于解决化工生产中的污染和资源利用问题、推动绿色有机合成化学的发展。

中文关键词： 过渡金属；3-氯芳基丙酮；烯酮；共轭加成；串联反应

英文摘要： Cross-coupling of organic halides has become one of the most important methods to form a carbon-carbon bond, in which iodides, bromides and some activated chlorides have been utilized as the coupling partners. Because it is usually difficult to activate an unactivated sp3 C-Cl bond, the cross-coupling of unactivated alkyl chlorides remains a challenging task in organic synthesis. In order to overcome this limitation, a domino reaction strategy is put forth to realize the transformations of unactivated alkyl chlorides by means of formation of the relatively reactive intermediates such as alpha,beta-unsaturated ketones and cyclopropyl ketones via beta or gamma-carbonyl directed sp3 C-Cl bond cleavage. In this indirect manner, transition metal-catalyzed cross-coupling of unactivated alkyl chlorides with other coupling partners can be used to construct diverse C-C and C-X bonds (X = B, N, O, S). Exploration of the related mechanisms will be carried out to understand the reaction sequences. The new methodology will be systematically investigated, providing a potential route to use unactivated alkyl chlorides for the cross-couplings in organic synthesis and giving fundamental understanding of unactivated alkyl chloride-involved domino reactions.

英文关键词： transition metals；3-chloropropyl aryl ketones；enones；conjugate addition；domino reactions