Foster Robert W, Benhamou Laure, Porter Michael J, Bučar Dejan-Krešimir, Hailes Helen C, Tame Christopher J, Sheppard Tom D
Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London, WC1H 0AJ (UK).
Chemistry. 2015 Apr 13;21(16):6107-14. doi: 10.1002/chem.201406286. Epub 2015 Mar 10.
The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promising lead-like properties for medicinal chemistry programs. Furthermore, the electron-rich furans are shown to react with a variety of alternative dienophiles to generate 7-oxabicyclo[2.2.1]heptane derivatives under mild conditions. DFT calculations have been performed to rationalize the activation effect of the 3-alkoxy group on a furan Diels-Alder reaction.
3-烷氧基呋喃与N-取代马来酰亚胺的[4+2]环加成反应为制备内型斑蝥酰亚胺提供了第一条通用路线。与3H呋喃的相应反应不同，该反应能够耐受多种2-取代呋喃，包括烷基、芳基和杂芳基。环加成产物被转化为一系列具有药用化学项目中类似先导物性质的斑蝥酰亚胺产物。此外，富电子呋喃在温和条件下能与多种替代亲双烯体反应生成7-氧杂双环[2.2.1]庚烷衍生物。已进行密度泛函理论（DFT）计算以阐明3-烷氧基对呋喃狄尔斯-阿尔德反应的活化作用。
