[闭式-1-CB9H10]阴离子的异构体纯1,10-双官能化衍生物的实用合成。

A practical synthesis of isomerically pure 1,10-difunctionalized derivatives of the [closo-1-CB9H10] anion.

作者信息

Ringstrand Bryan, Balinski Andrzej, Franken Andreas, Kaszynski Piotr

机构信息

Organic Materials Research Group, Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, USA.

出版信息

Inorg Chem. 2005 Dec 12;44(25):9561-6. doi: 10.1021/ic051311j.

DOI:10.1021/ic051311j

PMID:16323945

Abstract

The isomer-free [closo-1-CB9H(8)-1-COOH-10-I]- anion was prepared in four steps and 10% overall yield from B10H14. The key step is the skeletal isomerization of the [closo-2-CB9H8-2-COOH-7-I]- anion to a mixture of the 10- and 6-iodo derivatives of [closo-1-CB9H(9)-1-COOH]- formed in up to a 3:1 ratio. The carboxylic acid 4 was converted to the amine [closo-1-CB9H(8)-1-NH(2)-10-I]- using the Curtius reaction. The relative thermodynamic stability of each product was calculated at the DFT and MP2 levels of theory. The regioselectivity of electrophilic substitution in [closo-CB9H10]- derivatives was briefly investigated using the NBO population analysis of the MP2 wave function.

摘要

无异构体的[closo-1-CB9H(8)-1-COOH-10-I]-阴离子通过四个步骤由B10H14制备得到，总产率为10%。关键步骤是[closo-2-CB9H8-2-COOH-7-I]-阴离子的骨架异构化，生成比例高达3:1的[closo-1-CB9H(9)-1-COOH]-的10-碘和6-碘衍生物混合物。使用库尔提斯反应将羧酸4转化为胺[closo-1-CB9H(8)-1-NH(2)-10-I]-。在DFT和MP2理论水平上计算了每种产物的相对热力学稳定性。使用MP2波函数的NBO布居分析对[closo-CB9H10]-衍生物中亲电取代的区域选择性进行了简要研究。