Center for Advanced Technology, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 10, 61-614 Poznan, Poland.
Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland.
J Org Chem. 2022 Aug 19;87(16):10651-10663. doi: 10.1021/acs.joc.2c00844. Epub 2022 Aug 2.
A straightforward, efficient, and selective method for the preparation of novel boryl-functionalized enynes or dienes via [Pt(PPh)]-catalyzed diboration of a broad spectrum of symmetrical and unsymmetrical 1,3-diynes was developed. The catalytic cycle of diboration was proposed on the basis of low-temperature P NMR studies. An alternative isolation method via product condensation on a cold finger was developed, which, in contrast to previous literature reports, eliminates the need for the additional transformation of rapidly decomposing enynyl pinacol boronates to more stable silica-based column chromatography derivatives during the separation step. To prove the efficiency of this simple catalytic protocol, bisboryl-functionalized enynes were synthesized in a gram scale and tested as useful building blocks in advanced organic transformations, such as hydrosilylation and Suzuki and sila-Sonogashira couplings. The presence of silyl, boryl, as well as other functions like halogen or alkoxy in their structures builds a new class of multifunctionalized enynes that might be modified in various chemical reactions.
通过 [Pt(PPh)] 催化的广泛的对称和不对称 1,3-二炔的双硼化反应，开发了一种用于制备新型硼基官能化烯炔或二烯的直接、高效和选择性方法。根据低温 P NMR 研究提出了双硼化反应的催化循环。开发了一种通过在冷指上进行产物缩合的替代分离方法，与以前的文献报道相比，该方法在分离步骤中消除了将快速分解的烯炔基频哪醇硼酸酯转化为更稳定的基于硅胶的柱色谱衍生物的额外转化的需要。为了证明这种简单催化方案的效率，以克级规模合成了双硼基官能化的烯炔，并将其作为有用的构建块测试了在高级有机转化中的应用，如硅氢化、Suzuki 和硅烷-Sonogashira 偶联反应。其结构中存在硅基、硼基以及卤代或烷氧基等其他官能团，构建了一类新的多功能化烯炔，它们可以在各种化学反应中进行修饰。
