Das Pradip, Thakur Rima
Department of Chemistry, National Institute of Technology Patna, Patna 800 005, India.
Org Lett. 2023 Aug 18;25(32):6046-6051. doi: 10.1021/acs.orglett.3c02226. Epub 2023 Aug 9.
Ferrier rearrangement on glycals is an efficient tool to form 2,3-dideoxy glycosides that provide access to various sugar derivatives through olefin functionalization. The classical acid-mediated transformation delivers the α--glycosides selectively. In this protocol, amides obtained from amino acids, glycine and proline, have been utilized as sustainable β-directing leaving groups on glycal substrates. The directing groups facilitate β-selective Ferrier rearrangements for hard alcohol nucleophiles by following the Pd(0)-catalyzed Tsuji-Trost inner sphere pathway.
糖烯上的费里尔重排是形成2,3-二脱氧糖苷的有效工具，可通过烯烃官能化获得各种糖衍生物。经典的酸介导转化可选择性地生成α-糖苷。在本方法中，由氨基酸、甘氨酸和脯氨酸得到的酰胺被用作糖烯底物上可持续的β-导向离去基团。这些导向基团通过遵循钯(0)催化的辻-特罗斯特内球途径，促进了硬醇亲核试剂的β-选择性费里尔重排。
