An efficient method for selective oxidation of (oxime)Pt(II) to (oxime)Pt(IV) species using N,N-dichlorotosylamide

Abstract

The oxidation of (oxime)Pt II species using the electrophilic chlorine based oxidant N,N-dichlorotosylamide (4-CH3C6H4SO2NCl2) was studied. The reactions of trans-[PtCl2(oxime)2] (where oxime = acetoxime, cyclopentanone oxime, or acetaldoxime) with this oxidant lead to trans-[PtCl4(oxime)2] products. The oxidation of trans-[Pt(o-OC6H4CH=NOH)2] at room temperature gave trans-[PtCl2(o-OC6H4CH=NOH)2], whereas the same reaction upon heating was accompanied by electrophilic substitution of the benzene rings.

Halogenated PtIV Complexes from N‐Halosuccinimide Oxidation of PtII Antitumor Drugs: Synthesis, Mechanistic Investigation, and Cytotoxicity

“…Its low boiling point (–34 °C), high causticity, and high reactivity make it difficult to use in the laboratory. In order to avoid these issues, several electrophilic chlorinating reagents including iodobenzene dichloride (PhICl 2 ), N , N ‐dichlorobenzenesulfonamide (PhSO 2 NCl 2 ), and N , N ‐dichlorotosylamide have been utilized to obtain dichlorinated Pt IV complexes . These approaches, however, suffer from difficulties in the preparation of the chlorinating reagents, harsh reaction conditions, and high price, limiting their further use.…”

“…In order to avoid these issues, several electrophilic chlorinating reagents including iodobenzene dichloride (PhICl 2 ), N,Ndichlorobenzenesulfonamide (PhSO 2 NCl 2 ), and N,N-dichlorotosylamide have been utilized to obtain dichlorinated Pt IV complexes. [21][22][23] These approaches, however, suffer from difficulties in the preparation of the chlorinating reagents, harsh reaction conditions, and high price, limiting their further use. In previous reports, the addition of excess NCS to cis-[PtL 2 X 2 ] in methanol typically resulted in the generation of cis,cis,trans-[PtL 2 X 2 -(OCH 3 )Cl], where L is the N-donor ligand and X is the leaving group.…”