N-Alkenylation of hydroxamic acid derivatives with ethynyl benziodoxolone to synthesize cis-enamides through vinyl benziodoxolones. Issue 11 (5th March 2021)

• Record Type: Journal Article
• Authors: Shimbo, Daisuke; Maruyama, Toshifumi; Tada, Norihiro; Itoh, Akichika
• Is Part Of: Organic & biomolecular chemistry. Volume 19:Issue 11(2021)
• Page Start: 2442
• Page End: 2447
• Publication Date: 2021-03-05
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/d1ob00055a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Ethynyl benziodoxolone enabled the chemoselective N -functionalization of O -alkyl hydroxamic acids derived from amino acids and pharmaceuticals. The synthesized cis -vinyl benziodoxolone was derivatized to hydroxamic acid-derived enamides. Abstract : 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.