Preparation of cyclophanes by room-temperature ring-closing alkyne metathesis with imidazolin-2-iminato tungsten alkylidyne complexes

Room-temperature ring-closing alkyne metathesis of 1,2-, 1,3-, and 1,4-bis(3-pentynyloxymethyl)benzenes has been investigated in the presence of catalytic amounts of an imidazolin-2-iminato tungsten alkylidyne complex. The m- and p-diynes selectively form the respective [10]metacyclophane or [10.10]paracyclophane, respectively, whereas a mixture of monomeric and dimeric cycloalkynes is obtained in the case of the o-diyne. DFT calculations reveal that the different selectivities can be attributed to the relative thermodynamic stability of the emerging cyclophanes.