{[(meta‐Alkynylphenyl)alkenyl]carbene}chromium compounds 1 and 2 have been synthesized by four‐step (or five‐step) and seven‐step sequences, starting from 3‐halophenol or 3‐haloaniline, respectively. This approach, involving high‐yielding Takai reactions and lithium cuprate additions, provides a novel and straightforward route to [(alkynylaryl)alkenyl](methoxy)carbene complexes. Upon gentle warming in tetrahydrofuran, (carbene)chromium compounds of this type undergo intramolecular benzannulation to give novel [2.2]heterametacyclophanes 21 and 22, bearing two chiral planes arising from the unsymmetrical substitution patterns both of the cyclophane skeleton and of the newly formed, Cr(CO)3‐coordinated benzohydroquinone deck.

2002 organo-chromium compounds organo-chromium compounds S 5500 24 -188 Reactions of Complex Ligands. Part 93. Chromium-Templated Synthesis of Densely Substituted Distorted Arenes -Intramolecular Benzannulation of [(Alkynylaryl)alkenyl]carbene Complexes to Planar-Chiral Hydroquinoid [2.2]Heterametacyclophanes. -A novel and straightforward route to carbene complexes of type (VII) and (XV) is reported. On heating in THF they undergo intramolecular benzannulation to afford novel [2.2]heterametacyclophanes like (VIII) and (XVI) bearing two planes of chirality. -(DOETZ, K. H.; MITTENZWEY, S.; Eur. J.