Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan.
Org Biomol Chem. 2021 Mar 21;19(11):2442-2447. doi: 10.1039/d1ob00055a. Epub 2021 Mar 5.
The stereoselective synthesis of cis-β-N-alkoxyamidevinyl benziodoxolones (cis-β-N-RO-amide-VBXs) from O-alkyl hydroxamic acids in the presence of an ethynyl benziodoxolone-acetonitrile complex (EBX-MeCN) is reported herein. The reaction was performed under mild conditions including an aqueous solvent, a mild base, and room temperature. The reaction tolerated various O-alkyl hydroxamic acids derived from carboxylic acids, such as amino acids, pharmaceuticals, and natural products. Vinyl dideuterated cis-β-N-MeO-amide-VBXs were also synthesized using deuterium oxide as the deuterium source. Valine-derived cis-β-N-MeO-amide-VBX was stereospecifically derivatized to hydroxamic acid-derived cis-enamides without the loss of stereoselectivity or reduction in the deuterium/hydrogen ratio.
本文报道了在乙炔基苯并碘恶唑酮-乙腈络合物（EBX-MeCN）的存在下，从 O-烷基羟胺酸立体选择性合成顺式-β-N-烷氧基酰胺乙烯基苯并碘恶唑酮（cis-β-N-RO-酰胺-VBX）。该反应在温和的条件下进行，包括水溶剂、温和的碱和室温。该反应可以容忍各种 O-烷基羟胺酸，这些羟胺酸是由羧酸衍生而来的，如氨基酸、药物和天然产物。还使用重水作为氘源合成了氘代乙烯基顺式-β-N-MeO-酰胺-VBX。立体特异性地将缬氨酸衍生的顺式-β-N-MeO-酰胺-VBX 衍生为羟胺酸衍生的顺式-烯酰胺，而不会失去立体选择性或降低氘/氢比。
