硫代磺酸盐和二硫化物是生物活性分子和药物的重要支架,但从简单且可商业获得的原料开始并具有可持续路线的合成这些化合物的方法很少。在本报告中,我们提出了一种绿色方案,通过使用 H 2 O 2或空气作为氧化剂和阴离子多钼酸(Mo 8 O 26 4−)作为催化剂选择性氧化硫醇来合成这些有价值的 S-S 基序。该方法的显着特点是可扩展性、操作简单、广泛的功能组兼容性和良好的化学选择性。反应混合物的自由基捕获实验、动力学实验、循环伏安法、紫外-可见光谱、红外光谱和拉曼光谱监测等机理研究支持钼(V)-羟基物种和钼( VI )-过氧化合物的形成-分别驱动两个不同催化循环的物质。
The present invention relates to chirally controlled oligonucleotides, chirally controlled oligonucleotide compositions, and the method of making and using the same. The invention specifically encompasses the identification of the source of certain problems with prior methodologies for preparing chiral oligonucleotides, including problems that prohibit preparation of fully chirally controlled compositions, particularly compositions comprising a plurality of oligonucleotide types. In some embodiments, the present invention provides chirally controlled oligonucleotide compositions. In some embodiments, the present invention provides methods of making chirally controlled oligonucleotides and chirally controlled oligonucleotide compositions.