Shan Mingde, O'Doherty George A
Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
Org Lett. 2008 Aug 21;10(16):3381-4. doi: 10.1021/ol801106r. Epub 2008 Jul 18.
The stereoselective syntheses of 2,3-dideoxy-4-oxo-5a-carba-alpha- d-rhamnopyanose 1-phosphate, 2,3-dideoxy-5a-carba-alpha- d-rhamnopyranose 1-phosphate, 5a-carba-alpha- d-rhamnopyranose 1-phosphate, 5a-carba-beta- d-digitoxopyranose 1-phosphate, and 5a-carba-alpha- l-rhamnopyranose 1-phosphate have been achieved from d-quinic acid. The routes rely upon a Simmons-Smith cyclopropanation and diastereospecific ring opening of cyclopropanol under Pd/C hydrogenation condition to set up the alpha-methyl ketone. A sequence of diastereoselective reduction, dihydroxylation, and/or Myers' reductive 1,3-rearrangement were used to install the desired stereochemistry.
已从D-奎尼酸实现了2,3-二脱氧-4-氧代-5a-碳-α-D-鼠李吡喃糖1-磷酸酯、2,3-二脱氧-5a-碳-α-D-鼠李吡喃糖1-磷酸酯、5a-碳-α-D-鼠李吡喃糖1-磷酸酯、5a-碳-β-D-洋地黄毒糖吡喃糖1-磷酸酯和5a-碳-α-L-鼠李吡喃糖1-磷酸酯的立体选择性合成。这些路线依赖于Simmons-Smith环丙烷化反应以及在钯/碳氢化条件下环丙醇的非对映选择性开环以构建α-甲基酮。一系列非对映选择性还原、二羟基化和/或迈尔斯还原1,3-重排反应被用于引入所需的立体化学结构。
