Catalytic enantioselective alkylation of substituted dioxanone enol ethers:: Ready access to C(α)-tetrasubstituted hydroxyketones, acids, and esters
Catalytic enantioselective alkylation of substituted dioxanone enol ethers:: Ready access to C(α)-tetrasubstituted hydroxyketones, acids, and esters
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DOI：
10.1002/anie.200801424
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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：
--
作者：
Seto, Masaki;Roizen, Jennifer L.;Stoltz, Brian M.
四取代a-烷氧基化合物的催化对映体选择性形成对合成化学家来说是一个持续不断的挑战。[1]完全取代的a-羟基酯和酸是许多生物活性天然产物的基本成分和基本成分(见图1)。这些化合物包括奎宁酸(1)，细胞毒性的莱奥内酯A(2)，[2]和三尖杉酯碱系列的抗癌药物(3a-f)，它们的活性很大程度上取决于a-羟基酯侧链的存在和组成。[3]虽然有许多方法可以获得这些重要的部分，[4，5]我们设想将我们最近开发的钯催化的方法用于在环烷酮中形成富对映体的全碳四元立体中心[6]，以合成C(A)-四取代羟基羰基化合物[7]。
The catalytic enantioselective formation of tetrasubstituted a-alkoxycarbonyl compounds is an ongoing challenge to synthetic chemists.[1] Fully substituted a-hydroxyesters and acids comprise essential components of, and building blocks for, many bioactive natural products (see Figure 1). These include quinic acid (1), cytotoxic leiodolide A (2),[2] and the anticancer agents in the harringtonine series (3a–f), whose activities depend dramatically on the presence and composition of an a-hydroxyester side-chain.[3] While many approaches to these important moieties exist,[4, 5] we envisioned applying our recently developed palladium-catalyzed methods for the formation of enantioenriched all-carbon quaternary stereocenters in cyclic alkanones [6] to a general synthesis of C (a)-tetrasubstituted hydroxy carbonyl compounds.[7]