Functionalized nanodiamonds: triamantane and [121]tetramantane.
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.
Schreiner
Peter R
PR
Institut für Organische Chemie and Institut für Anorganische und Analytische Chemie, Justus-Liebig University, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany. prs@org.chimie.uni-giessen.de
Fokina
Natalie A
NA
Tkachenko
Boryslav A
BA
Hausmann
Heike
H
Serafin
Michael
M
Dahl
Jeremy E P
JE
Liu
Shenggao
S
Carlson
Robert M K
RM
Fokin
Andrey A
AA