Large P鈭扨 Distance Diphosphines and Their Monophosphine Analogues as Ligands in the Palladium-Catalyzed Telomerization of 1,3-Butadiene and Methanol

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• 作者：Mathieu J.-L. Tschan ; Josep-Maria Lo虂pez-Valbuena ; Zoraida Freixa ; He虂le虁ne Launay ; Henk Hagen ; Jordi Benet-Buchholz ; Piet W. N. M. van Leeuwen
• 刊名：Organometallics
• 出版年：2011
• 出版时间：February 28, 2011
• 年：2011
• 卷：30
• 期：4
• 页码：792-799
• 全文大小：892K
• 年卷期：v.30,no.4(February 28, 2011)
• ISSN：1520-6041

文摘

The potential of diphosphines based on a dibenzodioxocin or benzofurobenzofuran backbone possessing large P鈭扨 distances was studied for the selective telomerization of 1,3-butadiene with methanol under commercially relevant process conditions to obtain 1-methoxyocta-2,7-diene (1-MOD). They were found to act as monophosphines. New bulky monophosphine analogues of the same backbone and ferrocene were also evaluated. Several ligands showed improved selectivity and yield compared to the benchmark ligand PPh₃ and monoxantphos. Especially 1,6-bis(diphenylphosphino)-5a,10b-dihydro-5a,10b-dimethyl-3,8-dimethylbenzofuro[3,2-b]benzofuran (3) and, 2,10-di-tert-butyl-4-diphenylphosphino-6,12-methano-12H-dibenzo[2,1-d:1鈥?2鈥测€?g][1,3]dioxocin (7), a diphosphine and a monophosphine, respectively, stand out as excellent ligands in terms of yield, selectivity, and stability.