[123]Tetramantane: parent of a new family of sigma-helicenes.

ABSTRACT

We present a new type of sigma-helical structure based on a diamondoid (nanodiamond) framework, C(2)-symmetric [123]tetramantane, whose (+) and (-) isomers could be enantioseparated by HPLC techniques. Bromination of the enantiopure hydrocarbon led to the isolation of (+)-7-bromo-[123]tetramantane, which could be crystallized and subjected to X-ray structure analysis. Using the anomalous dispersion, we have identified this compound as the P isomer for the hydrocarbon moiety. Experimental and computed optical rotatory dispersion (ORD) and vibrational circular dichroism (VCD) spectra independently and in agreement with the X-ray structure analysis gave M-(-) as the configuration of the second eluted parent hydrocarbon isomer.