Low Catalyst Loading in the Cross Metathesis of Olefins with Methyl Vinyl Ketone

Muddasar Abbas; Anita Leitgeb; Christian Slugovc

doi:10.1055/s-0033-1338425

Synlett, Table of Contents

Synlett 2013; 24(10): 1193-1196
DOI: 10.1055/s-0033-1338425

cluster

Low Catalyst Loading in the Cross Metathesis of Olefins with Methyl Vinyl Ketone

Muddasar Abbas

^aForman Christian College, Ferozepur Road, 54600 Lahore, Pakistan

,

Anita Leitgeb

^bInstitute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria Fax: +43(316)8731032300 Email: slugovc@tugraz.at

,

Christian Slugovc*

^bInstitute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria Fax: +43(316)8731032300 Email: slugovc@tugraz.at

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Abstract

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Abstract

An olefin-metathesis catalyst featuring a 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene N-heterocyclic carbene and an ester-chelating carbene ligand efficiently promoted the cross metathesis of olefins with 3-buten-2-one in the presence of copper iodide as cocatalyst. At optimized reaction conditions a 10–20 times lower catalyst loading compared to the state of the art could be achieved.

Key words

catalysis - metathesis - enones - alkenes - ruthenium

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References

References and Notes

1a Handbook of Metathesis . Grubbs RH. Wiley-VCH; Weinheim: 2003
1b Prunet J. Eur. J. Org. Chem. 2011; 3634
1c Fischmeister C, Bruneau C. Beilstein J. Org. Chem. 2011; 7: 156
1d Nolan SP, Clavier H. Chem. Soc. Rev. 2010; 39: 3305

2a Wojtkielewicz A. Curr. Org. Synth. 2013; 10: 43
2b Schrodi Y, Pederson RL. Aldrichimica Acta 2007; 40: 45
2c Mori M. Adv. Synth. Catal. 2007; 349: 121
2d Grubbs RH. Angew. Chem. Int. Ed. 2006; 45: 3760
2e Grubbs RH, Trnka TM. Ruthenium-Catalyzed Olefin Metathesis . In Ruthenium in Organic Synthesis . Murahashi S.-I. Wiley-VCH; Weinheim: 2004
2f Diver ST, Giessert AJ. Chem. Rev. 2004; 104: 1317

3a Choi T.-L, Lee CW, Chatterjee AK, Grubbs R. J. Am. Chem. Soc. 2001; 123: 10417
3b Chatterjee AK, Choi T.-L, Sanders DP, Grubbs RH. J. Am. Chem. Soc. 2003; 125: 11360

4a Chatterjee AK, Morgan JP, Scholl M, Grubbs RH. J. Am. Chem. Soc. 2000; 122: 3783
4b Dewi P, Randl S, Blechert S. Tetrahedron Lett. 2005; 46: 577

5 Fernandes RA, Kattanguru P. Asian J. Org. Chem. 2013; 2: 74

6a Donohoe TJ, Bower JF. Proc. Natl. Acad. Sci. U.S.A. 2010; 107: 3373
6b Donohoe TJ, Bower JF, Chan LK. M. Org. Biomol. Chem. 2012; 10: 1322
6c Shafi S, Kędziorek M, Grela K. Synlett 2011; 124

7 Lesma G, Colombo A, Sacchetti A, Silvani A. J. Org. Chem. 2009; 74: 590
8 Fuwa H, Noto K, Sasaki M. Org. Lett. 2010; 12: 1636
9 BouzBouz S, Roche C, Cossy J. Synlett 2009; 803
10 Poulhes F, Sylvian R, Perfetti P, Bertrand MP, Gil G, Gastaldi S. Synthesis 2010; 1334

11a Henkie JR, Dhaliwal S, Green JR. Synlett 2012; 23: 2371
11b Murelli RP, Snapper ML. Org. Lett. 2007; 9: 1749

12a Wakamatsu H, Blechert S. Angew. Chem. Int. Ed. 2002; 41: 2403
12b Grela K, Harutyunyan S, Michrowska A. Angew. Chem. Int. Ed. 2002; 41: 4038
12c Rix D, Caijo F, Laurent I, Boeda F, Clavier H, Nolan SP, Mauduit M. J. Org. Chem. 2008; 73: 4225

13 Murray WC, Bargiggia FC. J. Org. Chem. 2005; 70: 9636

14a Chatterjee AK, Grubbs RH. Angew. Chem. Int. Ed. 2002; 41: 3172
14b Chatterjee AK, Toste FD, Choi T.-L, Grubbs RH. Adv. Synth. Catal. 2002; 344: 634

15a Voigtritter K, Ghorai S, Lipshutz H. J. Org. Chem. 2011; 76: 4697
15b Leong WW. Y, Taft BR, Ghorai S, Lipshutz H. J. Org. Chem. 2011; 76: 5061

16 Typical Experimental Procedure A Schlenk tube was charged with 1 (Fluka, 98%, 0.84 g, 9.98 mmol), 2 (Aldrich, 99%, stabilized with 1000 ppm BHT, 2.10 g, 0.0299 mol), and dry, degassed Et₂O (5 mL) under inert atmosphere of nitrogen. The reaction mixture was heated to 35 °C (oil bath temperature), the catalyst 6 (prepared according to ref. 18, 7.50 mg, 00998 mmol) was added, and the reaction mixture was kept at that temperature for 16 h. Afterwards, the reaction mixture was concentrated under reduced pressure to 1 mL and subjected to column chromatography (silica gel, eluent: cyclohexane). Drying of the appropriate fractions in vacuum yielded 3 as colorless oil in 92% yield. Reactions listed in Table 2 were carried out similarly. Always more than 90% isolated yield of the cross-metathesis products was obtained in all cases where full conversion was reached. Products were characterized by comparison of their chromatographic and spectroscopic with those described in the literature (ref. 3, 4, 15, and 18).

17a Abbas M, Slugovc C. Tetrahedron Lett. 2011; 52: 2560
17b Abbas M, Slugovc C. Monatsh. Chem. 2012; 143: 669

18 Leitgeb A, Abbas M, Fischer RC, Poater A, Cavallo L, Slugovc C. Catal. Sci. Technol. 2012; 2: 1640
19 Lin YA, Davis BG. Beilstein J. Org. Chem. 2010; 6: 1219
20 Ulman M, Belderrain TR, Grubbs RH. Tetrahedron Lett. 2000; 41: 4689

21a Borre E, Dinh TH, Caijo F, Crévisy C, Mauduit M. Synthesis 2011; 2125
21b Urbina-Blanco CA, Leitgeb A, Slugovc C, Bantreil X, Clavier H, Slawin AM. Z, Nolan SP. Chem. Eur. J. 2011; 17: 5045