Das Kuhali, Kundu Abhishek, Sarkar Koushik, Adhikari Debashis, Maji Biplab
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata Mohanpur 741246 India
Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali SAS Nagar 140306 India
Chem Sci. 2023 Dec 11;15(3):1098-1105. doi: 10.1039/d3sc05523j. eCollection 2024 Jan 17.
In this study, we employed a 3d metal complex as a catalyst to synthesize alkenyl boronate esters through the dehydrogenative coupling of styrenes and pinacolborane. The process generates hydrogen gas as the sole byproduct without requiring an acceptor, rendering it environmentally friendly and atom-efficient. This methodology demonstrated exceptional selectivity for dehydrogenative borylation over direct hydroboration. Additionally, it exhibited a preference for borylating aromatic alkenes over aliphatic ones. Notably, derivatives of natural products and bioactive molecules successfully underwent diversification using this approach. The alkenyl boronate esters served as precursors for the synthesis of various pharmaceuticals and potential anticancer agents. Our research involved comprehensive experimental and computational studies to elucidate the reaction pathway, highlighting the B-H bond cleavage as the rate-determining step. The catalyst's success was attributed to the hemilability and metal-ligand bifunctionality of the ligand backbone.
在本研究中，我们使用一种三维金属配合物作为催化剂，通过苯乙烯与频哪醇硼烷的脱氢偶联反应来合成烯基硼酸酯。该过程仅产生氢气作为唯一副产物，无需受体，使其具有环境友好性和原子经济性。这种方法在脱氢硼化反应中对直接硼氢化反应表现出卓越的选择性。此外，它对芳族烯烃的硼化反应优于脂肪族烯烃。值得注意的是，天然产物和生物活性分子的衍生物使用这种方法成功实现了多样化。烯基硼酸酯用作合成各种药物和潜在抗癌剂的前体。我们的研究涉及全面的实验和计算研究，以阐明反应途径，突出B-H键的裂解作为速率决定步骤。催化剂的成功归因于配体骨架的半不稳定和金属-配体双功能性。
