Catalytic asymmetric C-H activation of silyl enol ethers as an equivalent of an asymmetric Michael reaction
Catalytic asymmetric C-H activation of silyl enol ethers as an equivalent of an asymmetric Michael reaction
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DOI：
10.1021/ja0035607
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发表时间：
2001-03-07
影响因子：
15
通讯作者：
Ren, PD
中科院分区：
文献类型：
--
作者：
Davies, HML;Ren, PD
CH 激活化学选择性方法的发展将拓宽可用于合成复杂分子的策略范围。 1, 2 金属卡宾的 CH 插入化学是催化不对称 CH 活化的一种非常有吸引力的方法。 3 金属卡宾 CH 插入的对映选择性分子内版本已经很成熟。 4 最近，我们证明该反应的对映选择性分子间反应对于同时含有吸电子基团和给电子基团的铑卡宾也非常有效。 5 [Rh2 (S-DOSP) 4] 是这种转变的特殊手性催化剂。 6 此后，已有报道报道了烷烃、7 种烯烃、8 种多烯、9 种四氢呋喃、7 种 N-BOC 保护的环胺、10 种和烯丙基甲硅烷基醚 11 的高度对映选择性 CH 活化。 12 在本文中，我们描述了不对称 CH 活化在产品合成中的应用，这些产品通常源自不对称迈克尔反应。 13 关键步骤是在硅基烯醇醚存在下，Rh2 (S-DOSP) 4 催化芳基重氮乙酸甲酯分解（方程式 1）。
The development of chemoselective methods for CH activation would broaden the range of strategies that could be used for the synthesis of complex molecules. 1, 2 A very attractive method for catalytic asymmetric CH activation is the CH insertion chemistry of metal-carbenes. 3 The enantioselective intramolecular version of the metal-carbene CH insertion is well established. 4 Recently, we demonstrated that the enantioselective intermolecular version of this reaction is also very effective with rhodiumcarbenes containing both electron-withdrawing and electrondonating groups. 5 [Rh2 (S-DOSP) 4] is an exceptional chiral catalyst for this transformation. 6 Since then, highly enantioselective CH activation of alkanes, 7 alkenes, 8 polyenes, 9 tetrahydrofuran, 7 N-BOC protected cyclic amines, 10 and allyl silyl ethers11 have been reported. 12 In this paper we describe the application of the asymmetric CH activation to the synthesis of products that would be more typically derived from an asymmetric Michael reaction. 13 The key step is the Rh2 (S-DOSP) 4-catalyzed decomposition of methyl aryldiazoacetates in the presence of silyl enol ethers (eq 1).