英国布里斯托大学Varinder K. Aggarwal研究小组在有机合成研究中取得进展。他们实现了1,3-聚硼酯的高立体控制迭代合成，并将其用于合成bahamaolide A。2022年11月24日出版的《自然-化学》杂志发表了这项成果。

该研究团队报道了一种基于硼酯同源化的聚乙酸酯合成的高效迭代策略，在迭代之间不需要官能团操作。这一过程包括末端烯烃的连续不对称去硼化反应，生成1,2-二硼酯，然后伯硼酯与丁烯基金属卡宾基化合物之间发生区域和立体选择性同源化反应，生成1,3-二硼酯。该反应每一步转化都独立地控制着立体化学构型，使该过程具有高度的灵活性，并且在1,3-聚硼酸酯立体氧化生成1,3-多元醇之前，可以对反应进行迭代。

该方法已应用于14步合成含氧多烯大环内酯bahamaolide A，1,3-聚硼酯的灵活性已在各种立体定向转化中得到证明，可生成完全立体控制的聚烯烃、聚炔、聚酮和聚芳烃。

据介绍，聚酮天然产物常含有常见的重复结构，如丙酸、乙酸酯和脱氧丙酸等，可通过迭代法合成。

附：英文原文

Title: Iterative synthesis of 1,3-polyboronic esters with high stereocontrol and application to the synthesis of bahamaolide A

Author: Aiken, Sheenagh G., Bateman, Joseph M., Liao, Hsuan-Hung, Fawcett, Alexander, Bootwicha, Teerawut, Vincetti, Paolo, Myers, Eddie L., Noble, Adam, Aggarwal, Varinder K.

Issue&Volume: 2022-11-24

Abstract: Polyketide natural products often contain common repeat motifs, for example, propionate, acetate and deoxypropionate, and so can be synthesized by iterative processes. We report here a highly efficient iterative strategy for the synthesis of polyacetates based on boronic ester homologation that does not require functional group manipulation between iterations. This process involves sequential asymmetric diboration of a terminal alkene, forming a 1,2-bis(boronic ester), followed by regio- and stereoselective homologation of the primary boronic ester with a butenyl metallated carbenoid to generate a 1,3-bis(boronic ester). Each transformation independently controls the stereochemical configuration, making the process highly versatile, and the sequence can be iterated prior to stereospecific oxidation of the 1,3-polyboronic ester to yield the 1,3-polyol. This methodology has been applied to a 14-step synthesis of the oxopolyene macrolide bahamaolide A, and the versatility of the 1,3-polyboronic esters has been demonstrated in various stereospecific transformations, leading to polyalkenes, -alkynes, -ketones and -aromatics with full stereocontrol.

DOI: 10.1038/s41557-022-01087-9

Source: https://www.nature.com/articles/s41557-022-01087-9