A cascade process for directly converting nitriles (RCN) to cyanamides (RNHCN) via SO2F2-activated Tiemann rearrangement. Issue 33 (8th August 2019)

• Record Type: Journal Article
• Authors: Zhang, Guofu; Zhao, Yiyong; Ding, Chengrong
• Is Part Of: Organic & biomolecular chemistry. Volume 17:Issue 33(2019)
• Page Start: 7684
• Page End: 7688
• Publication Date: 2019-08-08
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c9ob01547g
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : A one-pot transition metal-free methodology for cyanamide preparation using readily available materials with easy work-up, wide substrate scope and great functional group-tolerability up to the gram scale. Abstract : A simple, mild and practical process for the direct conversion of nitriles to cyanamides was newly discovered and exhibited a wide substrate scope as well as great functional group-tolerability (36 examples). In this efficient strategy, the in situ generated amidoximes obtained from the reaction of nitriles with hydroxylamine subsequently underwent Tiemann rearrangement, producing the corresponding cyanamides with great isolated yields under SO2 F2 . Additionally, the control experiments reportedly shed light on the tentative mechanism involved in the formation and elimination of the key intermediate: a sulfonyl ester.