ChemInform Abstract: Evidence for Spontaneous, Low‐Temperature Biradical Formation from a Highly Reactive Neocarzinostatin Chromophore‐Thiol Conjugate.

Abstract

AbstractMethyl thioglycolate (II) adds to the antitumor antibiotic neocarzinostatin chromophore (I) to initially give (III), which is stable for days under argon at ‐70 °C. Intermediate (III) rapidly decays at ‐38 °C and above to produce the major products (VI) and (VII) via the monoradical (IV) and the diradical (V), resp., indicated by 2H incorporation at C‐2 and C‐6 of (VII) to the extent of 35 ±5% and at C‐2 of (VI) to the same degree.