Adak Souvik, Hazra Partha Sarathi, Fox Carter B, Brown M Kevin
Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, IN, 47401, US.
Angew Chem Int Ed Engl. 2025 Jan 21;64(4):e202416215. doi: 10.1002/anie.202416215. Epub 2024 Nov 7.
A strategy for the photosensitized [2+2]-cycloaddition between styrenyl dihaloboranes and unactivated allylamines to access cyclobutylboronates with control of stereochemistry and regiochemistry is presented. The success of the reaction relies on the temporary coordination between in situ generated dihaloboranes and amines under mild reaction conditions. In addition, cyclobutanes with varying substitution patterns have been prepared using N-heterocycles as directing group. Manipulation of the C-B bond allows for the synthesis of a diverse class of cyclobutanes from simple precursors. Moreover, these reactions lead to the synthesis of complex amines and heteroaromatic compounds, which have significant utility in medicinal chemistry. Finally, a dearomative [4+2]-cycloaddition of naphthalenes using a boron-enabled temporary tethering strategy has also been uncovered to synthesize complex 3-dimensional borylated building blocks.
本文提出了一种用于苯乙烯基二卤硼烷与未活化烯丙胺之间的光敏[2+2]环加成反应的策略，以制备具有立体化学和区域化学可控性的环丁基硼酸酯。该反应的成功依赖于在温和反应条件下原位生成的二卤硼烷与胺之间的临时配位。此外，使用氮杂环作为导向基团制备了具有不同取代模式的环丁烷。对碳-硼键的操作使得能够从简单前体合成多种类型的环丁烷。此外，这些反应还能合成复杂的胺类和杂芳族化合物，它们在药物化学中具有重要用途。最后，还发现了一种使用硼介导的临时连接策略对萘进行脱芳构化[4+2]环加成反应，以合成复杂的三维硼化结构单元。
