Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022, Jilin, PR China.
Org Lett. 2012 Mar 2;14(5):1218-21. doi: 10.1021/ol203444g. Epub 2012 Feb 9.
A novel protocol for the highly stereoselective synthesis of E,E-α,β,γ,δ-unsaturated dicarbonyl compounds is presented. Starting from the readily available allylic alcohols and 1,3-diketones, an array of E,E-α,β,γ,δ-dienones can be efficiently synthesized in high yields via Pd-catalyzed dehydrative allylation, H-migration, and aerobic oxidative δ-hydride elimination cascade. In addition to the novel reaction mechanism, the use of 1:1 allylic alcohol and 1,3-diketone as reactant, 5 mol % of PdCl(2) as catalyst, and 1 atm of environmentally benign O(2) as oxidant, as well as the generation of only H(2)O byproduct, makes this protocol rapid, simple, atom-efficient, and clean.
本文提出了一种新颖的高立体选择性合成 E,E-α,β,γ,δ-不饱和二羰基化合物的方案。以易得的烯丙基醇和 1,3-二酮为起始原料，通过 Pd 催化的脱水烯丙基化、H-迁移和有氧氧化 δ-氢消除级联反应，可以高效地合成一系列 E,E-α,β,γ,δ-二烯酮，产率很高。除了新颖的反应机制外，该方案还具有反应原料为 1:1 的烯丙基醇和 1,3-二酮、催化剂用量为 5 mol %的 PdCl(2)、环境友好的 1 atm O(2)作为氧化剂、仅生成 H(2)O 副产物等优点，因此该方案快速、简单、原子经济性好、清洁无污染。
