Synthesis of a Bent, Twisted, and Chiral Phenanthrene via an Iodine Monochloride-Mediated, Strain-Inducing π-Extension Reaction.

A strategy for the synthesis of substituted and strained p -phenylene units is reported. An oxidative allylic alcohol rearrangement, followed by organometallic addition to the resulting α-ketol and subsequent dehydrative aromatization, affords p -terphenyl-containing macrocycles in which the central p -phenylene has been selectively substituted. Ten 18-membered macrocycles have been synthesized, eight of which contain substituents that could enable π-extension. Only alkynylated derivatives were amenable to π-extension via an ICl-mediated reaction, affording a highly bent, twisted, and chiral phenanthrene.