Expanded scope in ethylene-alkyne cross-metathesis: Coordinating heteroatom functionality at the propargylic position

Organic Letters

Volumn 2, Issue 15, 2000, Pages 2271-2274

  Smulik, Jason A ^a   Diver, Steven T ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; CHELATING AGENT; ETHYLENE DERIVATIVE; RUTHENIUM DERIVATIVE;

ARTICLE; CATALYSIS; CHEMISTRY; KINETICS; METABOLISM; STEREOISOMERISM;

ALKYNES; CATALYSIS; CHELATING AGENTS; ETHYLENES; KINETICS; RUTHENIUM COMPOUNDS; STEREOISOMERISM;

EID: 0034720907     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol006035l     Document Type: Article

References (27)

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16. Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953.
17. Representitive Experimental Procedure for Alkyne-Ethylene Metathesis: (Table 2, entry 2). To an oven-dried pressure tube (90 mL capacity) equipped with a magnetic stirbar was added 41 mg (50 μmol, 5 mol %) of 1,3-dimesityl-4,5-dihydroimidazol-2-ylidenetricyclohexylphosphine benzylidene ruthenium dichloride (ref 7) under argon. A solution of 174 mg of 11b (1.0 mmol) in 4.0 mL of DCM was added to the catalyst via syringe, and the vessel was pressurized with 60 psi of ethylene (CP grade, 99.5%, Matheson) under rapid stirring. The pressure was released, and the vessel was flushed five times and then maintained at 60 psi of ethylene for 2 h. The pressure was released and the solvent removed in vacuo (rotary evaporator) to afford a dark brown oil which was purified by flash chromatography (1:4 ethyl acetate-hexanes). The product was obtained as an oil, 185 mg, 92% yield. Analytical TLC: Rf0.44 (1:4 ethyl acetate-hexanes). Spectra were identical to those reported in ref 3.
18. Trace styrene could be detected. No higher molecular weight products, such as dimers, were observed.
19. For instance, conversion of 11a (Table 2, entry 1) in the presence of 1 equiv of mesitylene internal standard was 99% after 2 h as measured using a calibrated GC method. The crude reaction mixture was subjected to column chromatography to remove the ruthenium catalyst. Fractions containing 11a were combined after purification which indicated 80% yield with respect to internal standard as judged by GC analysis.
20. The corresponding alcohol of 17 was less reactive giving only 44% conversion (GC) after 18 h.
21. Higher effective molarity of alkene in RCM applications likely improves the probability that alkene will bind to the metal leading to productive metathesis.
22. Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100.
23. Mori, M.; Sakakibara, N,; Kinoshita, A. J. Org. Chem. 1998, 63, 6082.
24. We make the distinction between the presence of alcohols (for which many metathesis applications are already known, see ref 5e) and the presence of alcohols in a potentially coordinating position with respect to intermediate ruthenium alkylidenes.
25. For the stability of the closely related ruthenium complex containing the imidazolylidene carbene ligand, see: Ulman, M.; Grubbs, R. H. J. Org. Chem. 1999, 64, 7202.
26. Enantiomeric excesses were measured by gc using a Chiradex-B capillary column (40-200 °C over 20 min, J & W Scientific, 0.25 mm × 30 m, 0.25 mm film thickness).
27. Diver, S. T.; Ahsan, K.; Smulik, J. A., unpublished data.