N-(2-Hydroxymethylphenyl)pyrrole was found to be amenable to selective a-metalation. Trapping with a variety of electrophilic reagents afforded the expected products with moderate to high yields. Derivatives formed by treatment of the organometahic intermediate with aldehydes, ketones or carbon dioxide could be cychzed to give pyrrolobenzoxazepines. Like many other benzo annelated two-ring heterocycles ['I, the ~,6Wpyrrolo[l,2-~][4,l]be nzoxawpine core (1) may be considered as a "pharmacophore". Members of the isomeric family of 5iY,llWpyrrok@,lc][l,4]ben~oxazepines (2) exhibit antinociceptive (hence analgesic) and central nervous system depressive activity fl, 21. The structurally related imidazo[l$-a][l,4]benzodiazepin~ in particular Flumazenit (3), are competitive antagonists of the benzodiazepine (e.g., diazepam) receptor f3]. The standard preparation of the 4I-Z,6H-pyrrolo[1,2-u][4,l]benzoxazepine ring system is based on the acid catalyzed attachment of a reactive carbonyl compound, for example ethyl pyruvate, to the a-position of N-(hydroxymethylphenyl)pyrrole (4) followed by cychzation. The reported over-ah yields are poor (c 30%). H,C-E-COOCH3 0 -{HeI 4 207 1 2072 M. SCHLOSSER and F. FAIGL It should be possible to carry out such condensation reactions more efficiently and to eztend its scope to less electrophilic carbonyl components if the pyrrole precursor could be metalated at the a-po&ion. This would immensely and selectively inaease the nudeoph.ilicity of the a-carbon site. In a previous study *41 we have identified reaction conditions that allow to carry out a nearly quantitatiw a-monometalation of IV-phenylpyrrole. Crucia for the success was to avoid the accumulation of o,a&meta&ted species the formation of which is