The Center for Precision Synthesis (CPS), Institute for Advanced Studies (IAS), Wuhan University, Wuhan, 430072, P. R. China.
Angew Chem Int Ed Engl. 2021 Mar 22;60(13):7405-7411. doi: 10.1002/anie.202014632. Epub 2021 Feb 11.
Catalytic alkene difunctionalization is a powerful strategy for the rapid assembly of complex molecules and has wide range of applications in synthetic chemistry. Despite significant progress, a compelling challenge that still needs to be solved is the installation of highly functionalized C(sp )-hybridized centers without requiring pre-activated substrates. We herein report that inexpensive and easy-to-synthesize decatungstate photo-HAT, in combination with nickel catalysis, provides a versatile platform for three-component alkene difunctionalization through direct and selective activation of aliphatic C-H bonds. Compared with previous studies, the significant advantages of this strategy are that the most abundant hydrocarbons are used as feedstocks, and various highly functionalized tertiary, secondary, and primary C(sp )-hybrid centers can be easily installed. The practicability of this strategy is demonstrated in the selective late-stage functionalization of natural products and the concise synthesis of pharmaceutically relevant molecules including Piragliatin.
催化烯烃双官能化是快速构建复杂分子的有力策略，在合成化学中有广泛的应用。尽管已经取得了显著的进展，但仍存在一个亟待解决的挑战性问题，即如何在无需预先活化底物的情况下，引入高官能化的 C(sp )-杂化中心。在此，我们报告廉价且易于合成的十钨酸盐光氢原子转移（photo-HAT）试剂，与镍催化相结合，通过直接和选择性地活化脂肪族 C-H 键，为三组分烯烃双官能化提供了一个通用的平台。与先前的研究相比，该策略的显著优势在于，最丰富的碳氢化合物被用作原料，并且可以轻松地引入各种高官能化的叔、仲和伯 C(sp )-杂化中心。该策略的实用性在天然产物的选择性后期官能化以及包括吡格列汀在内的具有药物相关性的分子的简洁合成中得到了证明。
