Decyanative Cross‐Coupling of Cyanopyrimidines with O‐, S‐, and N‐Nucleophiles: A Route to Alkoxylpyrimidines, Aminopyrimidines and Alkylthiopyrimidines. Issue 42 (16th October 2019)

• Record Type: Journal Article
• Authors: Wei, Xiangyang; Zhang, Caiyang; Wang, Yifei; Zhan, Qi; Qiu, Guiying; Fan, Ling; Yin, Guodong
• Is Part Of: European journal of organic chemistry. Issue 42(2019)
• Page Start: 7142
• Page End: 7150
• Publication Date: 2019-10-16
• Subjects: Cyanides -- Nitrogen heterocycles -- Nucleophilic substitution -- Synthetic methods; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201901364
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : The transition metal‐free cross‐coupling reactions of cyanopyrimidines with aliphatic alcohols, thiols (or S ‐alkylisothiourea salts) and amines, giving the corresponding alkoxylpyrimidines, aminopyrimidines, and alkylthiopyrimidines, are reported. Preliminary mechanistic studies reveal that it probably involves a sequential nucleophilic addition‐intramolecular rearrangement process, which is promoted by an intramolecular N–H··· N five‐membered hydrogen bonding interaction. The presence of a nitrogen atom next to the cyano group is indispensable. The wide substrate scope with excellent yields makes cyanopyrimidines a promising alternative substrate class to the frequently used pyrimidines halides for the formation of C–O, C–S, and C–N bonds through the decyanative cross‐coupling reaction. Abstract : A cross‐coupling reaction of cyanopyrimidines with aliphatic alcohols, thiols (or S‐alkylisothiourea salts) or amines gives the corresponding alkoxylpyrimidines, aminopyrimidines or alkylthiopyrimidines. The wide substrate scope with excellent yields makes cyanopyrimidines a promising alternative substrate class to the frequently used pyrimidines halides for the formation of C–O, C–S, and C–N bonds.