1,x-elimination reactions: extending the limits of a classical organic reaction.
Alpha,omega-dibromo derivatives in which the two terminal carbon atom are separated by an unsaturated spacer unit ("pi spacer") undergo 1,x-elimination reactions (with x=6, 8, 10, and 14), using Mori's reagent (nBu3SnSiMe3/CsF). The resulting cumulenic intermediates cyclodimerize in a subsequent step yielding novel macrocyclic acetylenic and bridged aromatic compounds (cyclophanes). Thus 1,6-eliminations were carried out with dibromide 17 to yield 1,3,7,9-cyclododecatetrayne (20) and with benzylbromide 24 to provide cyclophanes 26 and 27. By 1,8-eliminations the 16-membered macrocycle 33 could be prepared from enediyne 31, the benzannelated 1,5-cyclooctadiyne 41 from dibromide 38, and a mixture of cyclophanes 45 and 46 from the precursor 43. 1,10-Eliminations were carried out successfully with dibromides 47, 50, and 53 yielding the corresponding unsaturated cyclophanes ("cyclophynes") 49, 52, and 55. The influence of the solvent on the cyclodimerization 47-->49 was investigated, with acetonitrile providing the highest yields. The heterophanes 59 a and b were obtained by 1,10-elimination of the precursor dibromides 57 a and b, and in an elimination experiment involving a 1:1 mixture of the dibromides 50 and 57 b the "mixed dimer" 60 was isolated, besides the homodimers 52 and 59 b. The method reached its limits with the 1,14-elimination of 68, 70, and 74 providing the cyclophanes 69, 71, and 75 in varying amounts. Two final debrominations with 76 and 77, which in principle could undergo 1,16- and 1,20-eliminations reactions, respectively, failed. The structures of the new cyclophanes 49, 50, 59 a, and 59 b were established by X-ray structural analysis; all other structure assignments rest on the usual spectroscopic and analytical data.
Werner
Christian
C
Institut für Organische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.
Hopf
Henning
H
Dix
Ina
I
Bubenitschek
Peter
P
Jones
Peter G
PG