Enantioselective Nitroso‐Diels–Alder Reaction and Its Application for the Synthesis of (−)‐Peracetylated Conduramine A‐1 |
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| Authors: | Chandan Kumar Jana Dr. Stefan Grimme Prof. Dr. Armido Studer Prof. Dr. |
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| Affiliation: | NRW Graduate School of Chemistry, Organisch‐Chemisches Institut, Westf?lische Wilhelms‐Universit?t, Correnstrasse 40, 48149 Münster (Germany), Fax: (+49)?281‐83‐36523 |
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| Abstract: | CuI‐catalyzed enantioselective nitroso‐Diels–Alder reactions (NDA reactions) of 2‐nitrosopyridine with various dienes are presented. The [CuPF6(MeCN)4]/Walphos‐CF3 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. |
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| Keywords: | copper density functional calculations Diels– Alder reaction enantioselective catalysis natural products |
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