Stereospecific Intramolecular Arylation of 2- and 3-Pyridyl Substituted Alkylamines via Configurationally Stable α-Pyridyl Organolithiums

详细信息    查看全文

• 作者：Julien Maury ; Wojciech Zawodny ; Jonathan Clayden
• 刊名：Organic Letters
• 出版年：2017
• 出版时间：February 3, 2017
• 年：2017
• 卷：19
• 期：3
• 页码：472-475
• 全文大小：451K
• ISSN：1523-7052

文摘

Treatment of N′-aryl urea derivatives of enantiomerically enriched α-(2-pyridyl) and α-(3-pyridyl)alkylamines with a base leads to the migration of the N′-aryl substituent from N to C in a ‘nonclassical’ intramolecular nucleophilic aromatic substitution reaction. Both electron-rich and -poor rings migrate successfully. A new quaternary stereogenic center is formed adjacent to the pyridine ring with high stereospecificity, even when the intermediate anion is a presumably planar 2-picolyllithium. Base hydrolysis of the urea gives enantiomerically enriched α-pyridylalkylamines.