|
|
|
| Highly active rhodium/phosphorus catalytic system for the hydroformylation of α-methylstyrene |
| Xue-Li Zhenga, Cong-Ye Zhenga, Fan-Ding Zhoua, Hai-Yan Fua, Mao-Lin Yuana, Rui-Xiang Lia, Bin Xub, Hua Chena |
a Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China;
b Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education, Zigong 643000, China |
|
|
|
|
Abstract Rhodium catalyzed hydroformylation of α-methylstyrene was investigated in the presence of monodentate phosphine ligands L1-L6. We found that the phosphine with good π-acceptability could efficiently improve the activity of the α-methylstyrene hydroformylation. The big steric hindrance of α-C in α-methylstyrene enhanced the regioselectivity towards the linear aldehyde, which resulted in 3-phenylbutanal as the predominant product (>99.0%). When tris(N-pyrrolyl)phosphine (L1) modified Rh(acac)(CO)2 was employed as the catalyst, the TOF could reach up to 5786 h-1 in the α-methylstyrene hydroformylation at relatively mild conditions (110℃, 6 MPa).
|
|
Received: 13 October 2015
Published: 25 January 2016
|
| Fund:The authors thank the financial support from the National Natural Science Foundation of China (No. 201202108), from the Opening Project of Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education (No. LZJ1402), and from the Sichuan university outstanding scholar research fund (No. 2015SCU04A05). |
|
Corresponding Authors:
Xue-Li Zheng, Hua Chen
E-mail: zhengxueli@scu.edu.cn;scuhchen@scu.edu.cn
|
|
|
|
| [1] |
A.C.J. Koeken, N.M.B. Smeets, A bulky phosphite modified rhodium catalyst for efficient hydroformylation of disubstituted alkenes and macromonomers in supercritical carbon dioxide, Catal. Sci. Tech. 3(2013) 1036-1045.
|
| [2] |
T.J. Kwok, D.J. Wink, Characterization and application of catalytic regioselective hydroformylation with a cationic bis(dioxaphospholane)rhodium catalyst precursor, Organometallics 12(1993) 1954-1959.
|
| [3] |
R. Jackstell, H. Klein, M. Beller, K.D. Wiese, D. Röttger, Synthesis of pyrrolyl-, indolyl-, and carbazolylphosphanes and their catalytic application as ligands in the hydroformylation of 2-pentene, Eur. J. Org. Chem. (2001) 3871-3877.
|
| [4] |
C.Y. Zheng, M. Mo, H.R. Liang, et al., Rhodium/bisphosphite catalytic system for hydroformylation of styrene and its derivatives, Appl. Organomet. Chem. 27(2013) 474-478.
|
| [5] |
P. Suomalainen, H.K. Reinius, H. Riihimaki, et al., Hydroformylation of 1-hexene and propene with in situ formed rhodium phosphine catalysts, J. Mol. Catal. A Chem. 169(2001) 67-78.
|
| [6] |
H. Gulyas, A. Szollosy, P. Szabo, P. Halmos, J. Bakos, Preparation of new sulfonated triarylphosphanes:control of the selectivity by structural assistance, Eur. J. Org. Chem. (2003) 2775-2781.
|
| [7] |
Y.G. Yan, X.W. Zhang, X.M. Zhang, A tetraphosphorus ligand for highly regioselective isomerization-hydroformylation of internal olefins, J. Am. Chem. Soc. 128(2006) 16058-16061.
|
| [8] |
E. Boymans, M. Janssen, C. Muller, M. Lutz, D. Vogt, Rh-catalyzed linear hydroformylation of styrene, Dalton Trans. 42(2012) 137-142.
|
|
|
|
