Synthesis of novel halopyridinylboronic acids and esters. Part 2: 2,4, or 5-Halopyridin-3-yl-boronic acids and esters

This paper describes a general method for the synthesis and the isolation of novel 2,4, or 5-halopyridin-3-yl-boronic acids and esters , , , , . These compounds are prepared taking into account a regioselective halogen–metal exchange using nBuLi or a regioselective ortho-lithiation using lithium diisopropylamide and subsequent quenching with triisopropylborate starting from appropriate mono or dihalopyridines. All substrates studied to date provided a single regioisomeric boronic acid or ester product. Additionally, these compounds have been found to undergo Pd-catalyzed coupling with a range of arylhalides and authorize a strategy to produce new pyridines libraries.