Telomerisation of Buta-1,3-diene and Methanol: Superiority of Chromanyl-Type Phosphines in the Dow Process for the Industrial Production of 1-MOD

• Published in: Chemistry : a European journal Vol. 17; no. 32; pp. 8922 - 8928
• Main Authors: Tschan, Mathieu J.-L., Launay, Hélène, Hagen, Henk, Benet-Buchholz, Jordi, van Leeuwen, Piet W. N. M.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-08-2011; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: carbenes; Chemistry; ligand design; palladium; phosphane ligands; telomerisation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201100684

Butadiene and methanol were telomerised in the presence of palladium catalysts with ligands containing 8‐diphenylphosphinochromane‐like substituents at phosphorus. MonoXantphos and monoSPANphos afforded the most active, stable and selective catalysts known to date under commercially relevant production conditions for 1‐methoxyocta‐2,7‐diene, the precursor to oct‐1‐ene.
MonoXantphos and monoSPANphos: Palladium catalysts with ligands containing 8‐diphenylphosphinochromane‐like substituents at phosphorus allowed efficient telomerisation of buta‐1,3‐diene and methanol (see scheme). MonoXantphos and monoSPANphos afforded the most active, stable and selective catalysts known to date under commercially relevant production conditions for 1‐methoxyocta‐2,7‐diene, the precursor to oct‐1‐ene.