Organometallics
Article
13C NMR (75 MHz, CDCl3) δ 171.6, 137.8, 134.1, 129.4, 129.0, 128.6,
128.5, 127.1, 126.6, 65.4, 41.5, 35.1; MS m/z 104 [C8H8]+. NMR data
are in accord with literature values.12a
Benzyl Benzoate. DCVC eluting with heptane containing 2%
increments of ethyl acetate per fraction gave the product as a slightly
yellow oil: 1H NMR (300 MHz, CDCl3) δ 8.16−8.09 (m, 2H), 7.61−
7.54 (m, 1H), 7.52−7.33 (m, 7H), 5.40 (s, 2H); 13C NMR (75 MHz,
CDCl3) δ 166.5, 136.1, 133.1, 130.2, 129.8, 128.7, 128.4, 128.3, 128.2,
66.7; MS m/z 212 [M]+. NMR data are in accord with literature
values.26
General Procedure for Ruthenium-Catalyzed Ester Forma-
tion. [RuCl2(IiPr)(p-cymene)]12a (11.5 mg, 0.025 mmol), PCy3
(12.6 mg, 0.045 mmol), and KOH (5.6 mg, 0.1 mmol) were placed
in an oven-dried Schlenk flask. The flask was evacuated and refilled
with argon three times. The primary alcohol (1 mmol; 0.5 mmol in the
case of a diol) in anhydrous mesitylene (1 mL) was added and the
reaction mixture refluxed for 18 h under an argon atmosphere. The
mixture was cooled to room temperature and purified directly by dry
column vacuum chromatography20 (DCVC).
Pentyl Pentanoate. DCVC eluting with pentane containing 2%
increments of ethyl acetate per fraction gave the product as a slightly
4-Methylbenzyl 4-Methylbenzoate. DCVC eluting with heptane
1
yellow oil: H NMR (300 MHz, CDCl3) δ 3.92 (t, J = 6.7 Hz, 2H),
containing 2% increments of ethyl acetate per fraction gave the
1
2.16 (t, J = 7.5 Hz, 2H), 1.62−1.40 (m, 4H), 1.32−1.11 (m, 6H),
0.91−0.70 (m, 6H); 13C NMR (75 MHz, CDCl3) δ 174.0, 64.4, 34.2,
28.4, 28.2, 27.2, 22.4, 22.4, 14.0, 13.8; MS m/z 173 [M + H]+. NMR
data are in accord with literature values.21
product as a slightly yellow oil: H NMR (300 MHz, CDCl3) δ 7.97
(d, J = 8.3 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.1 Hz, 2H),
7.20 (d, J = 8.4 Hz, 2H), 5.32 (s, 2H), 2.41 (s, 3H), 2.37 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 166.7, 143.8, 138.1, 133.3, 129.8, 129.4,
129.2, 128.4, 127.6, 66.6, 21.8, 21.3; MS m/z 240 [M]+. NMR data are
in accord with literature values.8a
Decyl Decanoate. DCVC eluting with heptane containing 2%
increments of ethyl acetate per fraction gave the product as a slightly
1
yellow oil: H NMR (300 MHz, CDCl3) δ 4.04 (t, J = 6.7 Hz, 2H),
4-Methoxybenzyl 4-Methoxybenzoate. DCVC eluting with hep-
2.27 (t, J = 7.5 Hz, 2H), 1.66−1.53 (m, 4H), 1.25 (m, 26H), 0.86 (t, J
= 6.6 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 174.1, 64.5, 34.5, 32.0,
32.0, 29.7, 29.7, 29.6, 29.5, 29.4, 29.4, 29.4, 29.3, 28.8, 26.1, 25.2, 22.8,
22.8, 14.2, 14.2; MS m/z 312 [M]+. NMR data are in accord with
literature values.22
Undecyl Undecanoate. DCVC eluting with heptane containing
2% increments of ethyl acetate per fraction gave the product as a
slightly yellow oil: 1H NMR (300 MHz, CDCl3) δ 4.04 (t, J = 6.7 Hz,
2H), 2.27 (t, J = 7.5 Hz, 2H), 1.69−1.50 (m, 4H), 1.25 (bs, 30H), 0.86
(t, J = 6.6 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 174.1, 64.5, 34.5,
32.0, 29.8, 29.7, 29.7, 29.7, 29.6, 29.5, 29.5, 29.4, 29.4, 29.3, 28.8, 26.1,
25.2, 22.8, 14.2, 14.2; MS m/z 340 [M]+. NMR data are in accord with
literature values.23
tane containing 2% increments of ethyl acetate per fraction gave the
product as a slightly yellow oil: H NMR (300 MHz, CDCl3) δ 8.02
1
(d, J = 9.0 Hz, 2H), 7.39 (d, J = 8.8 Hz, 2H), 6.92 (d, J = 3.4 Hz, 2H),
6.89 (d, J = 3.6 Hz, 2H), 5.27 (s, 2H), 3.84 (s, 3H), 3.81 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 166.4, 163.5, 159.7, 131.8, 130.1, 128.5,
122.8, 114.0, 113.7, 66.4, 55.5, 55.4; MS m/z 272 [M]+. NMR data are
in accord with literature values.5c
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectra. This material is available free of
2-Ethylhexyl 2-Ethylhexanoate. DCVC eluting with pentane
containing 2% increments of ethyl acetate per fraction gave the
product as a slightly yellow oil: H NMR (300 MHz, CDCl3) δ 3.97
AUTHOR INFORMATION
Corresponding Author
■
1
(d, J = 5.7 Hz, 2H), 2.31−2.17 (m, 1H), 1.64−1.10 (m, 17H), 0.95−
0.69 (m, 12H); 13C NMR (75 MHz, CDCl3) δ 176.7, 66.3, 47.7, 38.9,
32.0, 30.6, 29.8, 29.0, 25.7, 24.0, 23.1, 22.8, 14.1, 14.0, 12.0, 11.1; MS
m/z 257 [M + H]+. NMR data are in accord with literature values.23
2-Methylpentyl 2-Methylpentanoate. DCVC eluting with pen-
tane containing 2% increments of ethyl acetate per fraction gave the
product as a slightly yellow oil: 1H NMR (300 MHz, CDCl3) δ 4.01−
3.88 (m, 1H), 3.87−3.79 (m, 1H), 2.42 (dt, J = 13.8, 7.0 Hz, 1H),
1.86−1.70 (m, 1H), 1.70−1.55 (m, 1H), 1.44−1.20 (m, 7H), 1.12 (d,
J = 7.0 Hz, 3H), 0.95−0.79 (m, 9H); 13C NMR (75 MHz, CDCl3) δ
177.1, 69.2, 39.6, 39.6, 36.1, 35.7, 32.4, 20.5, 20.0, 17.2, 17.0, 17.0,
14.4, 14.1; MS m/z 201 [M + H]+. NMR data are in accord with
literature values.24
ACKNOWLEDGMENTS
■
We thank the Danish Council for Independent Research
Technology and Production Sciences for financial support.
REFERENCES
■
(1) Otera, J.; Nishikido, J. Esterification: Methods, Reactions, and
Applications; Wiley-VCH: Weinheim, Germany, 2010.
(2) Reddy, R. S.; Rosa, J. N.; Veiros, L. F.; Caddick, S.; Gois, P. M. P.
Org. Biomol. Chem. 2011, 9, 3126.
(3) (a) Yasukawa, T.; Miyamura, H.; Kobayashi, S. Chem. Asian J.
2011, 6, 621. (b) Marsden, C.; Taarning, E.; Hansen, D.; Johansen, L.;
Klitgaard, S. K.; Egeblad, K.; Christensen, C. H. Green Chem. 2008, 10,
168.
(4) (a) Arita, S.; Koike, T.; Kayaki, Y.; Ikariya, T. Chem. Asian J.
2008, 3, 1479. (b) Izumi, A.; Obora, Y.; Sakaguchi, S.; Ishii, Y.
Tetrahedron Lett. 2006, 47, 9199.
γ-Butyrolactone. DCVC eluting with heptane containing 10%
increments of ethyl acetate per fraction gave the product as a colorless
1
oil: H NMR (300 MHz, CDCl3) δ 4.31 (t, J = 7.0 Hz, 2H), 2.50−
2.41 (m, 2H), 2.29−2.17 (m, 2H); 13C NMR (75 MHz, CDCl3) δ
177.8, 68.6, 27.8, 22.2; MS m/z 86 [M]+. NMR data are in accord with
literature values.25
γ-Valerolactone. DCVC eluting with heptane containing 10%
(5) (a) Luo, F.; Pan, C.; Cheng, J.; Chen, F. Tetrahedron 2011, 67,
5878. (b) Liu, C.; Wang, J.; Meng, L.; Deng, Y.; Li, Y.; Lei, A. Angew.
Chem., Int. Ed. 2011, 50, 5144. (c) Gowrisankar, S.; Neumann, H.;
Beller, M. Angew. Chem., Int. Ed. 2011, 50, 5139.
(6) (a) Kaizuka, K.; Miyamura, H.; Kobayashi, S. J. Am. Chem. Soc.
2010, 132, 15096. (b) Xu, B.; Haubrich, J.; Freyschlag, C. G.; Madix,
R. J.; Friend, C. M. Chem. Sci. 2010, 1, 310. (c) Su, F.-Z.; Ni, J.; Sun,
H.; Cao, Y.; He, H.-Y.; Fan, K.-N. Chem.Eur. J. 2008, 14, 7131.
(d) Nielsen, I. S.; Taarning, E.; Egeblad, K.; Madsen, R.; Christensen,
C. H. Catal. Lett. 2007, 116, 35.
increments of ethyl acetate per fraction gave the product as a colorless
oil: H NMR (300 MHz, CDCl3) δ 4.62−4.50 (m, 1H), 2.50−2.43
1
(m, 2H), 2.35−2.23 (m, 1H), 1.82−1.68 (m, 1H), 1.32 (d, J = 6.2 Hz,
3H); 13C NMR (75 MHz, CDCl3) δ 177.2, 77.2, 29.6, 29.0, 21.0; MS
m/z 100 [M]+. NMR data are in accord with literature values.25
δ-Valerolactone. DCVC eluting with heptane containing 10%
increments of ethyl acetate per fraction gave the product as a colorless
oil: 1H NMR (300 MHz, CDCl3) δ 4.21 (t, J = 5.9 Hz, 2H), 2.42 (t, J
= 7.0 Hz, 2H), 1.88−1.65 (m, 4H); 13C NMR (75 MHz, CDCl3) δ
171.3, 69.3, 29.6, 22.1, 18.8; MS m/z 100 [M]+. NMR data are in
accord with literature values.25
́
(7) (a) del Pozo, C.; Iglesias, M.; Sanchez, F. Organometallics 2011,
Phenethyl 2-Phenylacetate. DCVC eluting with heptane contain-
30, 2180. (b) Owston, N. A.; Nixon, T. D.; Parker, A. J.; Whittlesey,
M. K.; Williams, J. M. J. Synthesis 2009, 1578. (c) Zhang, J.;
Gandelman, M.; Shimon, L. J. W.; Milstein, D. Dalton Trans. 2007,
107. (d) Zhang, J.; Leitus, G.; Ben-David, Y.; Milstein, D. J. Am. Chem.
ing 2% increments of ethyl acetate per fraction gave the product as a
1
slightly yellow oil: H NMR (300 MHz, CDCl3) δ 7.45−7.16 (m,
10H), 4.36 (t, J = 7.0 Hz, 2H), 3.65 (s, 2H), 2.96 (t, J = 7.0 Hz, 2H);
6047
dx.doi.org/10.1021/om200928b|Organometallics 2011, 30, 6044−6048