1,3-Dipolar cycloaddition of 2,6-dichlorobenzonitrile oxide to 2-methyl-N-confused porphyrin. Regio- and stereoselective synthesis and structural characterization of 2-aza-21-carbabacteriochlorin and resolution of 2-aza-21-carbachlorin enantiomers.

ABSTRACT

The 1,3-dipolar cycloaddition reaction of 2-methyl-N-confused porphyrin with 2,6-dichlorobenzonitrile oxide yielded four isomeric monoadducts of carbachlorin type and one diadduct of carbabacteriochlorin type. Two major carbachlorin products, constituting 82% of the monoadducts, were shown to be structural precursors of the unique 2-aza-21-carbabacteriochlorin. Enantiomers of the most abundant isomer of 2-aza-21-carbachlorin (55% of all carbachlorin products) have been resolved. The crystal structures of 2-aza-21-carbabacteriochlorin and the most abundant isomer of 2-aza-21-carbachlorin were characterized by X-ray diffraction.