Zhou Maoquan, O'Doherty George A
Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
J Org Chem. 2007 Mar 30;72(7):2485-93. doi: 10.1021/jo062534+. Epub 2007 Mar 6.
A highly enantioselective and straightforward route to trisaccharide natural products digoxose and digitoxin has been developed. Key to this approach is the iterative application of the palladium-catalyzed glycosylation reaction, reductive 1,3-transposition, diastereoselective dihydroxylation, and regioselective protection. The first total synthesis of natural product digoxose was accomplished in 19 total steps from achiral 2-acylfuran, and digitoxin was fashioned in 15 steps starting from digitoxigenin 2 and pyranone 8beta. This flexible synthetic strategy also allows for the preparation of mono- and disaccharide analogues of digoxose and digitoxin.
已开发出一条高度对映选择性且直接的路线来合成三糖天然产物洋地黄毒糖和地高辛。该方法的关键是钯催化糖基化反应、还原1,3-迁移、非对映选择性二羟基化和区域选择性保护的迭代应用。天然产物洋地黄毒糖的首次全合成从非手性的2-酰基呋喃经19步完成，地高辛则从洋地黄毒苷配基2和吡喃酮8β开始经15步合成。这种灵活的合成策略还允许制备洋地黄毒糖和地高辛的单糖和二糖类似物。
