Silyl Assistance in the Intramolecular Addition of Pyridyl Radicals onto Pyridines and Quinolines. Issue 10 (11th March 2016)

• Record Type: Journal Article
• Authors: Filace, Fabiana; Sánchez‐Murcia, Pedro A.; Sucunza, David; Pérez‐Redondo, Adrián; Álvarez‐Buílla, Julio; Gago, Federico; Burgos, Carolina
• Is Part Of: European journal of organic chemistry. Issue 10(2016)
• Page Start: 1891
• Page End: 1896
• Publication Date: 2016-03-11
• Subjects: Radical reactions -- Density functional calculations -- Nitrogen heterocycles -- Silanes; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201600170
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: The first example of a stable acylazinium salt obtained by an intramolecular acylpyridine‐centered radical attack on azine nitrogen atoms is reported. Depending on the relative position of the bromo substituent on the attacking aminopyridine ring, it is possible to obtain selectively either the N ‐attack product or a different C ‐attack derivative. A rationale for this pathway selectivity was obtained from quantum mechanical calculations. Abstract : The first example of a stable acylazinium salt obtained by an intramolecular radical attack on an azine nitrogen is reported. The relative position of the Br atom on the attacking aminopyridine ring determines whether the N ‐radical attack product or a different C ‐attack derivative is obtained. QM calculations indicate that the bulk of the tris(trimethylsilyl)silane imparts the selectivity.