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

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

• 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