近日，日本东京大学Motomu Kanai团队实现了环半缩醛与丁烯的可见光驱动立体发散烯丙化合成。这一研究成果发表在2025年10月16日出版的《科学》杂志上。

催化将丰富的碳氢化合物原料转化为结构复杂的高价值分子是有机合成领域的一个关键但具有挑战性的目标。关键的困难在于化学惰性原料的同时活化和精确的立体化学控制。

研究组报道了无保护环半缩醛与丁烯的催化立体发散烯丙化，实现聚丙酸酯的可编程合成——包括药物在内的生物活性化合物中普遍存在的特权结构基序。这种可见光驱动的选择性转化表现出广泛的官能团相容性，为1,3-多元醇提供了多个连续的立体中心，具有高收率和立体化学保真度。此外，该方法提供了一条简洁实用的途径，以最少的保护-去保护序列获得关键的天然产物中间体。该策略具有简化聚丙酸合成的潜力，同时减少了时间、成本和环境影响。

附：英文原文

Title: Visible light–driven stereodivergent allylation of cyclic hemiacetals with butene for polypropionate synthesis

Author: Hiroyasu Nakao, Mirja Md Mahamudul Hassan, Yusuke Nakamura, Moe Toyobe, Masahiro Higashi, Harunobu Mitsunuma, Motomu Kanai

Issue&Volume: 2025-10-16

Abstract: Catalytically transforming abundant hydrocarbon feedstocks into structurally complex, high-value molecules is a pivotal yet challenging goal in organic synthesis. The key difficulty lies in the simultaneous activation of chemically inert feedstocks and precise stereochemical control. Here, we report a catalytic stereodivergent allylation of unprotected cyclic hemiacetal aldols with butene, enabling the programmable synthesis of polypropionates—privileged structural motifs prevalent in biologically active compounds, including pharmaceuticals. This visible light–driven, selective transformation exhibits broad functional group compatibility, furnishing 1,3-polyols with multiple contiguous stereocenters in high yield and stereochemical fidelity. Moreover, this method provides a concise and practical route to key natural product intermediates with minimal protection–deprotection sequences. This strategy has the potential to streamline polypropionate synthesis while reducing the time, cost, and environmental impact.

DOI: adz0686

Source: https://www.science.org/doi/10.1126/science.adz0686