Laboratory for Bioorganic Chemistry, Sloan-Kettering Institute for Cancer Research, 1275 York Avenue, New York, New York 10065, USA.
J Am Chem Soc. 2012 Jun 27;134(25):10659-63. doi: 10.1021/ja303876e. Epub 2012 Jun 18.
α,β-Unsaturated imides, formylated at the nitrogen atom, comprise a new and valuable family of dienophiles for servicing Diels-Alder reactions. These systems are assembled through extension of recently discovered isonitrile chemistry to the domain of α,β-unsaturated acids. Cycloadditions are facilitated by Et(2)AlCl, presumably via chelation between the two carbonyl groups of the N-formyl amide. Applications of the isonitrile/Diels-Alder logic to the IMDA reaction, as well as methodologies to modify the N-formyl amide of the resultant cycloaddition product, are described. It is expected that this easily executed chemistry will provide a significant enhancement for application of Diels-Alder reactions to many synthetic targets.
α,β-不饱和酰亚胺，氮原子上甲酰化，构成了 Dienes-Alder 反应的一类新型且有价值的亲双烯体。这些体系是通过将最近发现的异腈化学扩展到α,β-不饱和酸领域而构建的。环加成反应通过 Et(2)AlCl 促进，可能是通过 N-甲酰酰胺的两个羰基之间的螯合作用。异腈/Dienes-Alder 逻辑在 IMDA 反应中的应用，以及修饰所得环加成产物的 N-甲酰酰胺的方法学，都有描述。预计这种易于执行的化学将为 Diels-Alder 反应在许多合成目标中的应用提供显著增强。
