Synthesis of Functionalized Cyclooctynes as Building Blocks for Non‐covalent Surface‐Orthogonal Chemistry

Abstract

Cyclooctynes substituted with functional groups capable for hydrogen bonding (amide, imide, carboxylic acid) have been synthesized. The 8‐membered ring was derived from cyclooctadiene, by Beckmann rearrangement or by ring‐closing metathesis. The transannular instability of a monocyclic cyclooctyne lactam was postulated. Three stable functionalized cyclooctynes obtained are candidates for a surface‐orthogonal layer‐by‐layer synthesis on semiconductor surfaces (in particular the Si(001) surface).