Copper-Catalyzed Borylation/Carboxylation of Alkenes and Alkynes with Carbon Dioxide

我们已经开发了第一个简单炔和烯烃与二氧化碳（CO2）催化硼羧化的例子。在n -杂环碳(NHC)-铜配合物为催化剂、LiOtBu为碱的条件下，不饱和底物与双（pinacolato）二硼和CO2 （1atm）的反应在温和条件下选择性地产生了新的β -硼内酯衍生物家族。该反应具有底物范围广、区域选择性和立体选择性高的特点。我们还成功地从相关nhc -铜配合物的逐步化学计量反应中分离和结构表征了一些关键的反应中间体。根据实验结果和合理分析，提出了当前反应的可能机理。这项关于炔的研究发表在《美国化学会杂志》上，并在SYNFACTS中强调了这一点。烯烃实验结果的手稿现在正在准备中。

We have developed the first example of catalytic boracarboxylation of simple alkynes and alkenes with carbon dioxide (CO2). In the presence of N-heterocyclic carbene (NHC)-copper complexes as a catalyst and LiOtBu as a base, the reaction of unsaturated substrates with bis(pinacolato)diboron and CO2 (1 atm) selectively affords a novel family of beta-boralactone derivatives under mild conditions. The current reaction shows broad substrate scope, high regio- and stereoselectivity for the preparation of multifunctionalized hydrocarbons. We have also successfully isolated and structurally characterized some key reaction intermediates from stepwise stoichiometric reactions of related NHC-copper complexes. Based on the experimental results and rational analysis, a possible mechanism of the current reaction is proposed. The work on alkynes has been published in Journal of American Chemical Society and highlighted in SYNFACTS. The manuscript of the results of alkenes is now in preparation.