Jana Chandan Kumar, Grimme Stefan, Studer Armido
NRW Graduate School of Chemistry, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstrasse 40, 48149 Münster, Germany.
Chemistry. 2009 Sep 14;15(36):9078-84. doi: 10.1002/chem.200901331.
Cu(I)-catalyzed enantioselective nitroso-Diels-Alder reactions (NDA reactions) of 2-nitrosopyridine with various dienes are presented. The [CuPF(6)(MeCN)(4)]/Walphos-CF(3) catalyst system is best suited to catalyze the NDA reaction of various dienes by using 2-nitrosopyridine as a dienophile. In most of the cases studied, cycloadducts are obtained in quantitative yield with very good to excellent enantioselectivities. Based on DFT calculations, a model to explain the stereochemical outcome of the NDA reaction is presented. Finally, an efficient short synthesis of (-)-peracetylated conduramine A-1 by applying the enantioselective NDA reaction as a key step is described.
本文介绍了Cu(I)催化的2-亚硝基吡啶与各种二烯的对映选择性亚硝基-狄尔斯-阿尔德反应（NDA反应）。[CuPF(6)(MeCN)(4)]/Walphos-CF(3)催化剂体系最适合以2-亚硝基吡啶作为亲双烯体来催化各种二烯的NDA反应。在大多数研究案例中，环加成产物以定量产率获得，对映选择性非常好至优异。基于密度泛函理论计算，提出了一个解释NDA反应立体化学结果的模型。最后，描述了通过将对映选择性NDA反应作为关键步骤，高效简短合成(-)-全乙酰化康杜拉明A-1的方法。
