A Practical Synthesis of Isomerically Pure 1,10-Difunctionalized Derivatives of the [closo-1-CB9H10] Anion

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• 作者：Bryan Ringstrand ; Andrzej Balinski ; Andreas Franken ; and Piotr Kaszynski
• 刊名：Inorganic Chemistry
• 出版年：2005
• 出版时间：December 12, 2005
• 年：2005
• 卷：44
• 期：25
• 页码：9561 - 9566
• 全文大小：199K
• 年卷期：v.44,no.25(December 12, 2005)
• ISSN：1520-510X

文摘

The isomer-free [closo-1-CB₉H₈-1-COOH-10-I]^- anion (4) was prepared in four steps and 10% overall yield fromB₁₀H₁₄. The key step is the skeletal isomerization of the [closo-2-CB₉H₈-2-COOH-7-I]^- anion (3) to a mixture of the10- and 6-iodo derivatives of [closo-1-CB₉H₉-1-COOH]^- formed in up to a 3:1 ratio. The carboxylic acid 4 wasconverted to the amine [closo-1-CB₉H₈-1-NH₂-10-I]^- (1) using the Curtius reaction. The relative thermodynamicstability of each product was calculated at the DFT and MP2 levels of theory. The regioselectivity of electrophilicsubstitution in [closo-CB₉H₁₀]^- derivatives was briefly investigated using the NBO population analysis of the MP2wave function.