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.

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( sp ³)–H 债券提供了一些解决方案，但地点多样性仍然是一个问题。烯烃异构化与（氧化）官能化的合并提供了一种理想的远程官能化方法，这将为位点多样性提供更多机会。但所报道的功能站点仍然有限，且集中于特定的终端位置和内部站点；新的选址功能化，包括多功能化，仍然是一个很大程度上尚未解决的挑战。在这里，我们描述了一种用于多位点可编程功能化的钯催化有氧氧化方法，涉及 C=C 双键和多个 C( sp ³)–H 键，通过控制烯烃异构化和氧化官能化之间的反应顺序的策略来形成末端烯烃。具体来说，已经实现了1-乙酰氧基化（抗马尔可夫尼科夫）、2-乙酰氧基化、1,2-二乙酰氧基化和1,2,3-三乙酰氧基化，并伴有可控远程烯基化。该方法使得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。