Pd-catalysed oxidative carbonylation of amino alcohols to N,N′-bis(hydroxyalkyl)ureas under mild conditions using molecular oxygen as the oxidant

Abstract A very simple method has been developed for the selective synthesis of symmetrical N,N ′ - bis(hydroxyalkyl)ureas, OC[NH-(CH 2 ) x -OH] 2 ( x  = 3–6), by oxidative carbonylation of α,ω-amino alcohols [3-aminopropanol (3-AP), 4-aminobutanol (4-AB), 5-aminopentanol (5-APe), 6-aminohexanol (6-AH)] with CO/O 2 mixtures (O 2  = 5 mol%) in the presence of Pd(II)/ligand/NEt 3 ·HI catalytic systems. The catalytic process takes place under very mild conditions ( p (CO/O 2 ) = 0.1 MPa; 303–333 K). The target products can be isolated in high yield through a very simple and straightforward procedure. The catalytic system can be easily recovered and recycled for several times. The influence of a few reaction parameters (nature of ancillary ligand and iodide co-catalyst, I/Pd molar ratio, etc.) on the catalytic activity has also been investigated and the main mechanistic features of the catalytic process fully elucidated.