Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (py^tbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h^-1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.

中文翻译：

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用于烯烃烷氧基羰基化的高活性和高效催化剂。

烯烃的羰基化反应是均相催化中最重要的工业过程。尽管在这种转化中取得了巨大的进步，但开发先进的催化剂体系以提高其活性并拓宽原料的范围对于新的实际应用仍然是必不可少的。在此，基于1,2-双（（叔丁基（吡啶-2-基）膦基）甲基）苯L3的钯催化剂（py ^tbpx）是经过合理设计和综合的。该系统的应用使得可以以优异的收率将空间位阻和苛刻的烯烃，包括所有的四，三和1，1-二取代的烯烃以及天然产物和药物进行常规的烷氧基羰基化，以得到所需的酯。工业上相关的本体乙烯以高活性（TON：> 1,425,000； TOF：开始18 h为44,000 h ^-1）和选择性（> 99％）官能化。鉴于其通用性和效率，我们希望该催化体系通过提供一种实用的合成工具，将几乎所有的烯烃转化为通用的酯产品，立即对化学工业和研究实验室产生影响。