Hexapole [9]Helicene

Angew Chem Int Ed Engl. 2019 Jan 8;58(2):587-591. doi: 10.1002/anie.201811706. Epub 2018 Dec 12.

Abstract

Herein we present the first hexapole [9]helicene (H9H). Co-catalyzed [2+2+2] cyclotrimerization of a dinaphthopyrene (DNP) functionalized alkyne provides the hexaaryl benzene precursor 2, which is transformed into H9H via a dehydrocyclization reaction. Formation of each embedded [9]helicene involves forging of a new C-C bond, which stitches together two [4]helicene subunits of the neighboring DNP blades, reminiscent of the initial method Martin developed for the preparation of [9]helicene in the 1960s. Single-crystal X-ray analysis of both 2 and H9H discloses their extremely distorted and crowded structural features. Chiral resolution, optical and electronic properties of H9H are also presented.

Keywords: chirality; helicene; nonplanar; steric hindrance.