Four new colored components of Streptomyces murayamaensis sp. nov. Hata et Ohtani, the producer of the kinamycins, have been isolated and their structures determined by a combination of mass spectral, high field NMR and biosynthetic techniques. The first compound with the benz[b]carbazole skeleton in the biosynthetic pathway of kinamycin D has been named "pre-kinamycin" (7). A keto-epoxide kinamycin intermediate has been labeled "keto-anhydrokinamycin" (9), and the 1'-monoacetate of kinamycin has been called kinamycin E (12). Natural production of deacetylkinamycin (13, now labeled kinamycin F) by S. murayamaensis has been confirmed by an isotope trapping experiment. The role of these new intermediates in kinamycin biosynthesis is discussed.