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. 2012 Jan 11;134(1):693-9.
doi: 10.1021/ja210225e. Epub 2011 Dec 9.

Improved ruthenium catalysts for Z-selective olefin metathesis

Benjamin K Keitz  1 , Koji Endo, Paresma R Patel, Myles B Herbert, Robert H Grubbs
Affiliations

Improved ruthenium catalysts for Z-selective olefin metathesis

Benjamin K Keitz et al. J Am Chem Soc. .

Erratum in

  • J Am Chem Soc. 2013 Feb 27;135(8):3300

Abstract

Several new C-H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products.

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Figures

Figure 1
Figure 1
Catalysts 1–11. Ar = 2,4,6-trimethylbenzene (7), 2,6-diethyl-4-methylbenzene (8), 2,6-dimethyl-4-methoxybenzene (9), 2,6-dimethyl-4-chlorobenzene (10). Mes = 2,4,6-trimethylbenzene. DIPP = 2,6-di-i-propylbenzene.
Figure 2
Figure 2
Solid-state structure of 7 with thermal ellipsoids drawn at 50% probability. Selected bond lengths (Å) for 7. C1-Ru: 1.961, C13-Ru: 2.057, C23-Ru: 1.838, O1-Ru: 2.320, O2-Ru: 2.367, O3-Ru: 2.209.
Figure 3
Figure 3
Time-course plot for the conversion (A) and selectivity (B) of homodimerization of 15 to 16 using catalysts 7–10. Conditions were 15 (1 mmol), catalyst (1 μmol), in THF (0.1 mL) at 35 °C. Data points and error bars were calculated from the average and standard deviation of three separate runs.
Scheme 1
Scheme 1
Preparation of catalysts 3–6.
Scheme 2
Scheme 2
Preparation of catalysts 7 and 11.
Scheme 3
Scheme 3
Synthesis of 28 using catalyst 7.
See this image and copyright information in PMC

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