Department of Chemistry, Vanderbilt University, Nashville, TN 37235 (USA).
Department of Chemistry, Middle Tennessee University, Murfreesboro, TN 37123 (USA).
Angew Chem Int Ed Engl. 2015 May 26;54(22):6576-81. doi: 10.1002/anie.201411858. Epub 2015 Apr 15.
A simple method for the functionalization of closo-borates closo-B10 H10 (1), closo-1-CB9 H10 (2), closo-B12 H12 (3), closo-1-CB11 H12 (4), and 3,3'-Co(1,2-C2 B9 H11 )2 (5) is described. Treatment of the anions and their derivatives with ArI(OAc)2 gave aryliodonium zwitterions, which were sufficiently stable for chromatographic purification. The reactions of these zwitterions with nucleophiles provided facile access to pyridinium, sulfonium, thiol, carbonitrile, acetoxy, and amino derivatives. The synthetic results are augmented by mechanistic considerations.
一种简单的功能化方法可用于 closo-硼酸盐 closo-B10 H10 (1)、closo-1-CB9 H10 (2)、closo-B12 H12 (3)、closo-1-CB11 H12 (4) 和 3,3'-Co(1,2-C2 B9 H11 )2 (5)。用 ArI(OAc)2 处理这些阴离子及其衍生物得到芳基碘鎓两性离子，其足够稳定可进行色谱纯化。这些两性离子与亲核试剂的反应为容易得到吡啶鎓、硫鎓、硫醇、氰基、乙酰氧基和氨基衍生物提供了便利途径。通过考虑反应机理，补充了合成结果。
