通过铱催化转移氢化实现呋喃甲醇和糠醛的对映选择性羰基烯丙基化、巴豆基化和叔戊基化。
Enantioselective carbonyl allylation, crotylation, and tert-prenylation of furan methanols and furfurals via iridium-catalyzed transfer hydrogenation.
机构信息
Organisch-Chemisches Institut Ruprecht-Karls-Universität Heidelberg, D-69120 Heidelberg, Germany.
出版信息
J Org Chem. 2010 Mar 5;75(5):1795-8. doi: 10.1021/jo902697g.
Abstract
5-Substituted-2-furan methanols 1a-c are subject to enantioselective carbonyl allylation, crotylation and tert-prenylation upon exposure to allyl acetate, alpha-methyl allyl acetate, or 1,1-dimethylallene in the presence of an ortho-cyclometalated iridium catalyst modified by (R)-Cl,MeO-BIPHEP, (R)-C3-TUNEPHOS, and (R)-C3-SEGPHOS, respectively. In the presence of 2-propanol, but under otherwise identical conditions, the corresponding substituted furfurals 2a-c are converted to identical products of allylation, crotylation, and tert-prenylation. Optically enriched products of carbonyl allylation, crotylation, and reverse prenylation 3b, 4b, and 5b were subjected to Achmatowicz rearrangement to furnish the corresponding gamma-hydroxy-beta-pyrones 6a-c, respectively, with negligible erosion of enantiomeric excess.
摘要
5-取代-2-呋喃甲醇 1a-c 在偕位环金属化铱催化剂的作用下，分别与醋酸烯丙酯、α-甲基烯丙基醋酸酯或 1,1-二甲基丙烯发生不对称羰基烯丙基化、巴豆基化和叔戊基化反应，该催化剂由 (R)-Cl,MeO-BIPHEP、(R)-C3-TUNEPHOS 和 (R)-C3-SEGPHOS 进行修饰。在 2-丙醇的存在下，但在其他相同条件下，相应的取代呋喃 2a-c 被转化为相同的烯丙基化、巴豆基化和叔戊基化产物。不对称羰基烯丙基化、巴豆基化和反向戊基化的光学富集产物 3b、4b 和 5b 分别进行 Achmatowicz 重排，得到相应的γ-羟基-β-吡喃酮 6a-c，对映体过量值几乎没有损失。
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