Aliphatic C−C Bond Cleavage in α‐Hydroxy Ketones by a Dioxygen‐Derived Nucleophilic Iron–Oxygen Oxidant. Issue 16 (27th February 2017)

• Record Type: Journal Article
• Authors: Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K.
• Is Part Of: Chemistry. Volume 23:Issue 16(2017)
• Page Start: 3815
• Page End: 3818
• Publication Date: 2017-02-27
• Subjects: C−C bond cleavage -- dioxygen -- iron -- nucleophilic oxidant -- α-hydroxy ketones; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201605672
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A nucleophilic iron–oxygen oxidant, formed in situ in the reaction between an iron(II)–benzilate complex and O2, oxidatively cleaves the aliphatic C−C bonds of α‐hydroxy ketones. In the cleavage reaction, α‐hydroxy ketones without any α‐C−H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C−C bond of 17‐α‐hydroxyprogesterone affording androstenedione and acetic acid. The O2 ‐dependent aliphatic C−C bond cleavage of α‐hydroxy ketones containing no α‐C−H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1). Abstract : Cleavage of aliphatic C−C bonds : A nucleophilic iron–oxygen oxidant from an iron(II)–benzilate complex cleaves the aliphatic C−C bonds of α‐hydroxy ketones including the C17−C20 lyase of 17‐α‐hydroxyprogesterone.