New Cobalt-Catalyzed Cross-Couplings and Electrophilic Aminations using Organozinc Reagents

将使用多官能团有机卤化物和有机锌试剂开发新的钴催化的交叉偶联，包括在主要是CSP³-CSP³中心之间形成新的碳-碳键。重点介绍非对映选择性和对映选择性交叉偶联的性能。将应用于天然产物的合成，如(-)-munduserone，以展示这一新方法的实用性。此外，还将研究一种新的钴催化的酰化反应方法，该方法使用的是有机丙戊酸锌和2-吡啶硫代酯。最后，我们将开发一种新的钴催化的亲电胺化反应，包括有机锌和卤化物与苯甲酸羟胺的反应。在本课题中，提供方便和高产率的羟胺苯甲酸酯制剂将是很重要的。由于钴的廉价和低毒性质(例如与钯相比)，本项目中描述的交叉偶联反应和胺化具有实际意义，应该成为学术界和工业界合成有机社区的有用工具。

The elaboration of new cobalt-catalyzed cross-couplings involving the formation of new carbon-carbon bonds between mainly Csp³-Csp³ centers will be developed using polyfunctional organic halides and organozinc reagents. The performance of diastereoselective and enantioselective cross-couplings will be emphasized. Applications in the synthesis of natural products such as (-)-munduserone will be done to demonstrate the utility of this new methodology. Also, a new cobalt-catalyzed acylation method using organozinc pivalates and 2-pyridyl thioesters will be studied. Finally, a new cobalt-catalyzed electrophilic amination involving the reaction of organozinc pivalates and halides with hydroxylamine benzoates will be developed. In this topic, it will be important to provide convenient and high yielding preparations of hydroxylamine benzoates. Due to the cheap and low toxic nature of cobalt (compared for example to palladium) the cross-coupling reactions and aminations described in this project have practical relevance and should become helpful tools for the synthetic organic community in the academic and industrial world.