上海交通大学张万斌团队报道了通过可控烯烃异构化的烯烃多位点可编程功能化。相关研究成果于2023年5月18日发表于国际顶尖学术期刊《自然—化学》。

烃链的直接和选择性官能化是合成化学中的一个基本问题。C=C双键和C（sp3）-H键的常规功能化提供了一些解决方案，但位点多样性仍然是一个问题。烯烃异构化与（氧化）官能化的结合为远程官能化提供了一种理想的方法，这将为位点多样性提供更多的机会。然而，所报道的功能化位点仍然有限，并且集中在特定的末端位置和内部位点；新的位点选择性功能化，包括多功能化，仍然是一个很大程度上未得到满足的挑战。

该文中，研究人员描述了一种钯催化的好氧氧化方法，用于通过控制烯烃异构化和氧化功能化之间的反应序列的策略进行末端烯烃的多位点可编程功能化，包括C=C双键和多个C（sp3）–H键。具体而言，已经实现了1-乙酰氧基化（抗Markovnikov）、2-乙酰氧基、1,2-二乙酰氧基和1,2,3-三乙酰氧基，并伴有可控的远程烯基化。该方法使来自石化原料的可用末端烯烃能够容易地转化为不饱和醇和多元醇，特别是转化为不同的单糖和C-糖苷。

附：英文原文

Title: Multi-site programmable functionalization of alkenes via controllable alkene isomerization

Author: Wu, Zhengxing, Meng, Jingjie, Liu, Huikang, Li, Yunyi, Zhang, Xiao, Zhang, Wanbin

Issue&Volume: 2023-05-18

Abstract: Direct and selective functionalization of hydrocarbon chains is a fundamental problem in synthetic chemistry. Conventional functionalization of C=C double bonds and C(sp3)–H bonds provides some solutions, but site diversity remains an issue. The merging of alkene isomerization with (oxidative) functionalization provides an ideal method for remote functionalization, which would provide more opportunities for site diversity. However, the reported functionalized sites are still limited and focus on a specific terminal position and internal site; new site-selective functionalization, including multi-functionalization, remains a largely unmet challenge. Here we describe a palladium-catalysed aerobic oxidative method for the multi-site programmable functionalization, involving the C=C double bond and multiple C(sp3)–H bonds, of terminal olefins via a strategy that controls the reaction sequence between alkene isomerization and oxidative functionalization. Specifically, 1-acetoxylation (anti-Markovnikov), 2-acetoxylation, 1,2-diacetoxylation and 1,2,3-triacetoxylation have been realized, accompanied by controllable remote alkenylation. This method enables available terminal olefins from petrochemical feedstocks to be readily converted into unsaturated alcohols and polyalcohols and particularly into different monosaccharides and C-glycosides.

DOI: 10.1038/s41557-023-01209-x

Source: https://www.nature.com/articles/s41557-023-01209-x