Molecular Addition Compounds. 18. Borane Adducts with Hydroxydialkyl Sulfide Borates for Hydroboration. New, Essentially Odorless, Water-Soluble Sulfide Borane Acceptors for Hydroboration
作者:Herbert C. Brown、Marek Zaidlewicz、Pramod V. Dalvi、Goutam K. Biswas
DOI:10.1021/jo010051u
日期:2001.7.1
used as borane carriers. The compounds 3 and 6 (R = Et, n = 2, 3), 7 (R = t-Bu, n = 3), and 9 are completely miscible with water and exhibit only very mild odor. The sulfides were transformed into the corresponding borates by treatment either with boric acid or with diborane. The borates complex 3 mol of borane per 1 mol of borate to give highly reactive, stable, liquid adducts, hydroborating 1-octene
已经合成了通式RS(CH 2 CH 2)n H(R = Et,t-Bu,i-Am; n = 1-3)的羟基二烷基硫化物和硫代二乙醇单甲醚(9),并用作硼烷载体。化合物3和6(R = Et,n = 2、3),7(R = t-Bu,n = 3)和9与水完全混溶,并且仅表现出非常温和的气味。通过用硼酸或乙硼烷处理将硫化物转化为相应的硼酸盐。硼酸盐与1摩尔硼酸盐形成3摩尔硼烷的络合物,可在室温下于15分钟内生成高反应性,稳定的液体加合物,对1-辛烯进行氢硼化。由水溶性硫化物3和9衍生的加合物,被选择用于受阻更多的烯烃的硼氢化反应,容易与(-)-β-pine烯,1-甲基环己烯和2,3-二甲基-2-丁烯反应。在加氢硼化期间从加合物中释放出的载体硼酸盐易于水解,得到3和9,可以用水将其从三烷基硼烷或氧化产物中洗掉。因此,羟基二烷基硫化物3和9是第一种完全水溶性的硫化硼烷载体,可以在加氢硼化产物的后处理中