K. Grela et al.
charged with the catalyst (0.03 mmol), and the requisite solvent was
added to prepare a stock solution (10 mL, [c]=0.003m). In this way, solu-
tions of all of the complexes (Gru-II, Ind-II, Ind-II’, Hov-II, Gre-II, and
Est-II) in both of the required solvents (dichloromethane and toluene)
were prepared. Such stock solutions should be used within a few hours
because prolonged storage, even in a glovebox, can lead to partial de-
composition of the catalysts.
CMof 1j or 1k with cis-1,4-diacetoxy-2-butene (3a): In a glovebox,
4 mL vials were charged with alkene (1j or k) stock solution ([c]=0.06m,
1 mL, 0.06 mmol), cross-metathesis partner (3a) stock solution ([c]=
0.12m, 1 mL, 0.12 mmol), and toluene (0.8 mL). The appropriate catalyst
stock solution ([c]=0.003m, 0.2 mL, 0.6 mmol) was then added to each
vial by means of an adjustable-volume pipette. As a result, six solutions
in toluene were obtained with the following parameters: concentration of
1j or k: [c]=0.02m; catalyst loading (Gru-II, Ind-II, Ind-II’, Hov-II, Gre-
II, and Est-II, respectively): 1 mol%; solution volume: 3 mL.
Alkenes for RCM(1a–f), enyne metathesis (1g–i), and CM(1j–o) : A
single stock solution containing enough substrate for metathesis reactions
with all six catalysts was prepared. In a glovebox, a volumetric flask was
charged with the appropriate diene (1a–f), enyne substrate (1g–i), or
alkene (1j–o) (0.6 mmol), along with dodecane (for alkenes 1a–i) or tet-
radecane (for alkenes 1j–o) (0.3 mmol) as an internal standard. The
requisite solvent was then added to prepare a stock solution (10 mL,
[c]=0.06m). In this way, solutions of all of the alkenes (1a–o) in both of
the required solvents (dichloromethane and toluene) were prepared. All
of these solutions could be stored in sealed vials under Ar for extended
periods of time.
CMof 1l, m, or n with cis-1,4-diacetoxy-2-butene (3a): In a glovebox,
4 mL vials were charged with alkene (1l, m, or n) stock solution ([c]=
0.06m, 1 mL, 0.06 mmol) and cross-metathesis partner (3a) stock solution
([c]=0.12m, 1 mL, 0.12 mmol). The appropriate catalyst stock solution
([c]=0.003m, 1 mL, 3 mmol) was then added to each vial by means of an
adjustable-volume pipette. As a result, six solutions in toluene were ob-
tained with the following parameters: concentration of 1l, m, or n: [c]=
0.02m; catalyst loading (Gru-II, Ind-II, Ind-II’, Hov-II, Gre-II, and Est-II,
respectively): 5 mol%; solution volume: 3 mL.
CMof 1o with methyl acrylate (3b) : In a glovebox, 4 mL vials were
charged with alkene (1o) stock solution ([c]=0.06m, 1 mL, 0.06 mmol),
cross-metathesis partner (3b) stock solution ([c]=0.12m, 1 mL,
0.12 mmol), and toluene (0.96 mL). The appropriate catalyst stock solu-
tion ([c]=0.003m, 0.04 mL, 0.012 mmol) was then added to each vial by
means of an adjustable-volume pipette. As a result, six solutions in tolu-
ene were obtained with the following parameters: concentration of 1o:
[c]=0.02m; catalyst loading (Gru-II, Ind-II, Ind-II’, Hov-II, Gre-II, and
Est-II, respectively): 0.2 mol%; solution volume: 3 mL.
Cross-metathesis (CM) partners (3a–d): In a glovebox, a volumetric flask
was charged with the appropriate alkene (3a–c) (1.2 mmol) or (3d)
(2.4 mmol), and then toluene was added to prepare a stock solution
(10 mL, [c]=0.12m) and (10 mL, [c]=0.24m), respectively. All of these
solutions could be stored in sealed vials under Ar for extended periods
of time.
RCMof 1a–c, and f : In a glovebox, 4 mL vials were charged with alkene
(1a, b, c, or f) stock solution ([c]=0.06m, 1 mL, 0.06 mmol) and the re-
quired solvent (1.8 mL). The appropriate catalyst stock solution ([c]=
0.003m, 0.2 mL, 0.6 mmol) was then added to each vial by means of an ad-
justable-volume pipette. As a result, six solutions in dichloromethane and
six solutions in toluene were obtained with the following parameters:
concentration of 1a, b, c, or f: [c]=0.02m; catalyst loading (Gru-II, Ind-
II, Ind-II’, Hov-II, Gre-II, and Est-II, respectively): 1 mol%; solution
volume: 3 mL. To obtain solutions with catalyst loadings of 0.05, 0.02,
and 0.005 mol%, the appropriate catalyst stock solutions were diluted ac-
cording to the following procedure. Aliquots of 0.5, 0.2, and 0.05 mL of
the appropriate catalyst stock solution ([c]=0.003m) were added by
means of an adjustable-volume pipette to volumetric flasks and the ap-
propriate solvent was added to prepare new stock solutions (10 mL) with
catalyst concentrations [c]=0.15, 0.06, and 0.015 mm, respectively. The
thus prepared diluted catalyst stock solutions were used to prepare reac-
tion mixtures with the required catalyst loadings of 0.05, 0.02, and
0.005 mol%, respectively.
CMof 1o with phenyl vinyl sulfone (3c) : In a glovebox, 4 mL vials were
charged with alkene (1o) stock solution ([c]=0.06m, 1 mL, 0.06 mmol),
cross-metathesis partner (3c) stock solution ([c]=0.12m, 1 mL,
0.12 mmol), and toluene (0.8 mL). The appropriate catalyst stock solution
([c]=0.003m, 0.2 mL, 0.6 mmol) was then added to each vial by means of
an adjustable-volume pipette. As a result, six solutions in toluene were
obtained with the following parameters: concentration of 1o: [c]=0.02m;
catalyst loading (Gru-II, Ind-II, Ind-II’, Hov-II, Gre-II, and Est-II, re-
spectively): 1 mol%; solution volume: 3 mL.
CMof 1o with 2-methylacrylonitrile (3d) : In a glovebox, 4 mL vials were
charged with alkene (1o) stock solution ([c]=0.06m, 1 mL, 0.06 mmol)
and cross-metathesis partner (3d) stock solution ([c]=0.24m, 1 mL,
0.24 mmol). The appropriate catalyst stock solution ([c]=0.003m, 1 mL,
3 mmol) was then added to each vial by means of an adjustable-volume
pipette. As a result, six solutions in toluene were obtained with the fol-
lowing parameters: concentration of 1o: [c]=0.02m; catalyst loading
(Gru-II, Ind-II, Ind-II’, Hov-II, Gre-II, and Est-II, respectively): 5 mol%;
solution volume: 3 mL.
RCMof 1d and e : In a glovebox, 4 mL vials were charged with alkene
(1d or e) stock solution ([c]=0.06m, 1 mL, 0.06 mmol) and the required
solvent (1 mL). The appropriate catalyst stock solution ([c]=0.003m,
1 mL, 3 mmol) was then added to each vial by means of an adjustable-
volume pipette. As a result, six solutions in dichloromethane and six solu-
tions in toluene were obtained with the following parameters: concentra-
tion of 1d or 1e: [c]=0.02m; catalyst loading (Gru-II, Ind-II, Ind-II’,
Hov-II, Gre-II, and Est-II, respectively): 5 mol%; solution volume:
3 mL.
GC data analysis: Samples for GC analysis were obtained by adding ali-
quots of about 200 mL of the reaction mixtures to 500 mL of a 2m solution
of ethyl vinyl ether in dichloromethane.[59] All aliquots were taken auto-
matically at the specified times by the Vantage device. The samples were
shaken and then analysed by GC. To obtain accurate yield data, the FID
detector response factors were obtained for all the key products (ethyl-
ene excluded). Tetradecane was used as the internal standard for CM re-
actions, whereas for RCM and enyne metathesis dodecane was employed.
The responses of the FIDdetector were calibrated using 2a/dodecane,
2b/dodecane, 2c/dodecane, 2d/dodecane, 2e/dodecane, 2 f/dodecane, 2g/
dodecane, 2h/dodecane, 2i/dodecane, 2n/tetradecane, 2o/tetradecane,
and 2r/tetradecane standard solutions, respectively. All products required
for this calibration were synthesised and isolated according to literature
procedures.
Enyne metathesis of 1h: In a glovebox, 4 mL vials were charged with
alkene (1h) stock solution ([c]=0.06m, 1 mL, 0.06 mmol) and the re-
quired solvent (1.8 mL). The appropriate catalyst stock solution ([c]=
0.003m, 0.2 mL, 0.6 mmol) was then added to each vial by means of an ad-
justable-volume pipette. As a result, six solutions in toluene were ob-
tained with the following parameters: concentration of 1h: [c]=0.02m;
catalyst loading (Gru-II, Ind-II, Ind-II’, Hov-II, Gre-II, and Est-II, re-
spectively): 1 mol%; solution volume: 3 mL.
Enyne metathesis of 1i: In a glovebox, 4 mL vials were charged with
enyne substrate (1i) stock solution ([c]=0.06m, 1 mL, 0.06 mmol) and
solvent (1 mL). The appropriate catalyst stock solution ([c]=0.003m,
1 mL, 3 mmol) was then added to each vial by means of an adjustable-
volume pipette. As a result, six solutions in dichloromethane and six solu-
tions in toluene were obtained with the following parameters: concentra-
tion of 1i: [c]=0.02m; catalyst loading (Gru-II, Ind-II, Ind-II’, Hov-II,
Gre-II, and Est-II, respectively): 5 mol%; solution volume: 3 mL.
Acknowledgements
Research support by the Polish Academy of Sciences (President of Polish
Academy of Sciences Fellowship to M. Bieniek) is gratefully acknowl-
edged. We wish to thank Dr. Bartłomiej Furman for providing alkene
816
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 806 – 818