Cycloparaphenylenes (CPPs) are a remarkable class of hoop-shaped conjugated macrocycles with inimitable properties. Herein we describe a divergent synthesis of [7]CPP and [8]CPP. Furthermore we present the first crystal structure of [7]CPP. Thus, we have now established the size-selective synthesis of [n]CPP (n = 7-16) in a uniformed cyclohexane-based method.

The paper describes the addition of Mg‐anilides and ‐thiolates to in situ generated benzyne with subsequent oxidative homocoupling of the adducts to give 2,2′‐bis‐substituted biphenyls in a one‐pot process. Oxidative C–C bond formation was best achieved with a Cu catalyst using O2 as oxidant. The sequence comprises two C–X and one C–C bond formation and the products were obtained in moderate yields. Some of the 2,2′‐bis‐substituted biphenyls have been characterized by X‐ray analysis.

In a first step, Mg anilides or thiolates are added to benzyne, generated in situ from precursor (I).