Palladium-catalyzed enantioselective oxidation of chiral secondary alcohols: Access to both enantiomeric series
Palladium-catalyzed enantioselective oxidation of chiral secondary alcohols: Access to both enantiomeric series
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DOI：
10.1002/anie.200801865
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Stoltz, Brian M.
中科院分区：
文献类型：
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作者：
Ebner, David C.;Trend, Raissa M.;Stoltz, Brian M.
富含对映体的醇广泛存在于天然产物和药物的结构和合成中。[1]以前，我们报道了在分子氧存在下，通过催化[Pd(Nbd)Cl2](1，nbd=降冰片二烯)和天然生成的生物碱(−)-司马汀(sp，(−)-2)来催化醇类化合物的有氧动力学拆分的发展。[2-6]尽管该体系成功地将多种仲醇拆分为高对映体过量，但某些底物的氧化速度非常慢。此外，使用2作为配体(仅作为(−)对映体在商业上可用)限制了对映体系列中的醇的访问。[7]在此，我们公开了一种基于对反应机理的理解而开发的催化剂，该反应机理导致反应速率显著增加，从而
Enantioenriched alcohols are ubiquitous in the structures and syntheses of natural products and pharmaceuticals. Catalytic, asymmetric alcohol oxidation can be a useful method to access these molecules.[1] Previously, we reported the development of an aerobic kinetic resolution of alcohols by catalytic [Pd (nbd) Cl2](1, nbd= norbornadiene) and the naturally occurring alkaloid (−)-sparteine (sp,(−)-2) in the presence of molecular oxygen.[2-6] Although this system successfully resolves a wide range of secondary alcohols to high enantiomeric excess, the rates of oxidation for certain substrates are prohibitively slow. Furthermore, the use of 2 as a ligand, which is only commercially available as the (−)-antipode, restricts access to alcohols in one enantiomeric series.[7] Herein, we disclose the development of a catalyst based on an understanding of reaction mechanism that effects dramatic rate increases, thereby