DOI: 10.1039/C4CC05626D
Page 3 of 4
Journal Name
ChemComm
COMMUNICATION
Then, the effects of partial pressure and catalyst loading on the
model reaction were studied. As shown in Table 2, the activity of the
osmium-catalyst is very sensitive towards the partial pressure
although the regioselectivity was not affected (Table 2, entries 1-6).
Besides, reducing the catalyst loading gave somewhat lower yields.
Electronic Supplementary Information (ESI) available: [General
procedure, ligands and aldehydes characterization data]. See
DOI: 10.1039/c000000x/
1
C. Döbler, G. M. Mehltretter, U. Sundermeier, M. Beller, J. Am.
Chem. Soc. 2000, 122, 10289-10297.
(a) B. S. Pilgrim, T. J. Donohoe, J. Org. Chem., 2013, 78, 2149-2167;
Investigations of the influence of the solvent revealed that the
osmium-catalyzed hydroformylation proceeds better in polar
solvents.
Acetonitrile,
propylene
carbonate
(PC)
and
2
dimethylacetamide (DMA) are all suitable solvents for this
transformation leading to similar yields and slightly different side-
products distributions (Table S1, entries 1-5). THF or non-polar
toluene showed a gradual decrease of the aldehyde yield with
decreased solvent polarity (Table S1, entries 6-7).
(b) R. A. Sanchez-Delgado, B. A. Oramas, J. Mol. Catal. 1986, 36, 283-
291.
3
(a) A. Varela-Fernández, C. García-Yebra, J. A. Varela, M. A.
Esteruelas, C. Saá, Angew. Chem. Int. Ed., 2010, 49, 4278-4281; (b) M.
Batuecas, M. A. Esteruelas, C. García-Yebra, E. Oñate, Organometallics
2010, 29, 2166-2175; (c) M. A. Esteruelas, T. Garcıa-Obregón, J.
́
Herrero, M. Oliván, Organometallics 2011, 30, 6402-6407.
4
(a) R. Castarlenas, M. A. Esteruelas, E. Oñate, Organometallics
2005, 24, 4343-4346; (b) S. Díez-González, N. Marion, S. P. Nolan,
Chem. Rev. 2009, 109, 3612-3676.
5
(a) R. Castarlenas, M. A. Esteruelas, E. Oñate, Organometallics
2008, 27, 3240-3247; (b) W. Baratta, F. Benedetti, A. Del Zotto, L.
Fanfoni, F. Felluga, S. Magnolia, E. Putignano, P. Rigo, Organometallics
2010, 29, 3563-3570; (c) W. Baratta, C. Barbato, S. Magnolia, K. Siega,
P. Rigo, Chem. Eur. J. 2010, 16, 3201-3206.
6
M. L. Buil, V. Cadierno, M. A. Esteruelas, J. Gimeno, J. Herrero, S.
Izquierdo, E. Oñate, Organometallics 2012, 31, 6861-6867.
M. A. Esteruelas, N. Honczek, M. Olivꢀn, E. Oꢁate, M. Valencia,
Organometallics 2011, 30, 2468-2471.
W. Baratta, M. Ballico, G. Chelucci, K. Siega, P. Rigo, Angew.
Scheme 3. Osmium-catalyzed hydroformylation of different alkenes: 3.2
mmol olefins, Os3(CO)12 0.5 mol%, L3 1.65 mol%, 2 mL acetonitrile, CO/H2
30:30 bar, 130 °C, 20 h (only major products are shown).
7
8
Finally, the scope and limitations of this novel osmium-
catalyzed hydroformylation reaction were examined with industrially Chem. Int. Ed., 2008, 47, 4362-4365.
important aliphatic as well as various functionalized olefins (Scheme
3). For the linear aliphatic alkenes, the yields of the aldehydes
increased with decreased chain length (Scheme 3, 1, 4-5).
Nevertheless, the high regioselectivity for all cases retained the
same. Alkenes which cannot undergo isomerization side reactions
gave up to 87% aldehydes yield (Scheme 3, 6 and 7). For styrene,
the thermodynamic stability of the intermediate osmium η3-allyl
intermediate reduced the linear selectivity to 68% (Scheme 3, 8).
Besides, functionalized alkenes such as methyl methacrylate reacted
well (Scheme 3, 9). Hex-5-en-1-ol also gave the corresponding
product in good yield and regioselectivity (Scheme 3, 10).
9
W. Baratta, G. Bossi, E. Putignano, P. Rigo, Chem. Eur. J. 2011, 17
,
,
,
3474-3481.
10 D. Spasyuk, S. Smith, D. G. Gusev, Angew. Chem. Int. Ed., 2012, 51
2772-2775.
11 P. Barrio, M. A. Esteruelas, E. Oñate, Organometallics 2004, 23
1340-1348.
12 R. A. Sanchez-Delgado, A. Andriollo, N. Valencia, J. Chem. Soc.,
Chem. Commun. 1983, 444-445.
13 H. Marrakchi, J.-B. Nguini Effa, M. Haimeur, J. Lieto, J.-P. Aune, J.
Mol. Catal. 1985, 30, 101-109.
14 (a) X. Jia, Z. Wang, C. Xia, K. Ding, Chem. Eur. J. 2012, 18, 15288-
15295; (b) L. Garcia, C. Claver, M. Dieguez, A. M. Masdeu-Bulto, Chem.
Commun. 2006, 191-193; (c) L. A. van der Veen, P. C. J. Kamer, P. W.
N. M. van Leeuwen, Organometallics 1999, 18, 4765-4777; (d) M.
In summary, we have developed for the first time a highly
regioselective osmium-catalyzed hydroformylation of olefins. The
catalytic system consists of Os3(CO)12 and imidazoyl-substituted
phosphine ligands, which in-situ form the active species. High linear
selectivity is observed for both industrial bulk aliphatic alkenes as
well as functional alkenes.
Janssen, J. Wilting, C. Muller, D. Vogt, Angew. Chem. Int. Ed., 2010, 49
7738-7741; (e) R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112
5675-5732.
,
,
We are grateful to the funding support from the State of
Mecklenburg-Vorpommern, BMBF, Alexander von Humboldt
Foundation (grants for Q.L.) and the analytic department in
Likat. We also acknowledge Dr. Christoph Kubis from Likat
for his kind help for IR measurements.
15 B. Breit, in Metal Catalyzed Reductive C–C Bond Formation, Vol.
279 (Ed.: M. Krische), Springer Berlin Heidelberg, 2007, pp. 139-172.
16 J. Pospech, I. Fleischer, R. Franke, S. Buchholz, M. Beller, Angew.
Chem. Int. Ed., 2013, 52, 2852-2872.
17 (a) J. Norinder, C. Rodrigues, A. Börner, J. Mol. Catal. A: Chem.
2014, 391, 139-143; (b) K. Takahashi, M. Yamashita, Y. Tanaka, K.
Nozaki, Angew. Chem. Int. Ed., 2012, 51, 4383-4387; (c) I. Fleischer, L.
Notes and references
aLeibniz-Institut für Katalyse an der Universität Rostock, Albert-Einstein-
Str. 29a, 18059 Rostock, Germany.
Wu, I. Profir, R. Jackstell, R. Franke, M. Beller, Chem. Eur. J. 2013, 19
,
10589-10594; (d) L. Wu, I. Fleischer, R. Jackstell, I. Profir, R. Franke, M.
Beller, J. Am. Chem. Soc. 2013, 135, 14306-14312; (e) L. Wu, I.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3