Functionalized nanodiamonds: triamantane and [121]tetramantane.
Functionalized nanodiamonds: triamantane and [121]tetramantane.
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功能化纳米金刚石：三金刚烷和[121]四金刚烷。
DOI：
10.1021/jo052646l
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
A. Fokin
中科院分区：
文献类型：
--
作者：
P. Schreiner;N. Fokina;B. Tkachenko;H. Hausmann;M. Serafin;J. Dahl;Shenggao Liu;R. Carlson;A. Fokin
阐述了基本的氢封端的纳米金刚石三金刚烷1以及四金刚烷（C（2 h）-[121]四金刚烷2）的最对称的代表的选择性官能化。亲电试剂（Br 2，HNO 3）主要攻击中间的C-H位置的笼;溴化2得到的中间2-溴衍生物几乎完全。在1和2中的高选择性顶端取代是可能的，无论是在单电子转移氧化通过烃基阳离子或通过与双乙酰的光乙酰化。1和2的单-和双-乙酰基衍生物通过Bayer-Villiger氧化和随后的水解转化为相应的顶端单-和二羟基衍生物。这种特殊的合成特异性有助于将2，也许是更大的纳米金刚石分子转化为广泛应用所需的功能化结构单元，如纳米技术。
The selective functionalizations of the fundamental hydrogen-terminated nanodiamonds triamantane 1, as well as the most symmetrical representative of the tetramantanes (C(2h)-[121]tetramantane 2) were elaborated. Electrophilic reagents (Br2, HNO3) predominantly attack the medial C-H positions of the cages; bromination of 2 gave the medial 2-bromo derivative almost exclusively. Highly selective apical substitution in 1 and 2 is possible either under single-electron-transfer oxidations via hydrocarbon radical cations or through photoacetylation with diacetyl. The mono- and the bis-acetyl derivatives of 1 and 2 were converted through Bayer-Villiger oxidation and subsequent hydrolysis to the respective apical mono- and dihydroxy derivatives. This exceptional synthetic specificity facilitates the transformation of 2, and perhaps larger nanodiamond molecules, into functionalized building blocks needed for a wide range of applications such as nanotechnology.