The Journal of Organic Chemistry
Note
Isopropyl (S)-2-Hydroxy-4-phenylpent-4-enoate (1c). 101 mg,
86% yield. 1H NMR (400 MHz, CDCl3) δ: 7.47−7.39 (m, 2H), 7.38−
7.31 (m, 2H), 7.31−7.26 (m, 1H), 5.39 (d, J = 1.2 Hz, 1H), 5.21 (dd, J
= 2.3, 1.2 Hz, 1H), 4.99 (hept, J = 6.3 Hz, 1H), 4.23 (ddd, J = 7.7, 6.2,
4.6 Hz, 1H), 3.06 (ddd, J = 14.5, 4.5, 1.0 Hz, 1H), 2.80 (ddd, J = 14.5,
7.8, 0.9 Hz, 1H), 2.71 (d, J = 6.2 Hz, 1H), 1.23 (d, J = 6.3 Hz, 3H),
1.21 (d, J = 6.3 Hz, 3H). HPLC (OJ-H, 95% hexanes, 5% i-PrOH, 1.0
mL/min, 254 nm): 89% ee, 8.7 min (major), 11.5 min (minor). The
compound had been fully characterized previously.6a
ASSOCIATED CONTENT
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S
* Supporting Information
1
Copies of H and 13C NMR spectra for new compounds and
chiral HPLC analyses. This material is available free of charge
AUTHOR INFORMATION
Corresponding Author
Notes
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Ethyl (S)-2-Hydroxy-4-p-tolylpent-4-enoate (1d). 110 mg, 94%
1
yield. H NMR (400 MHz, CDCl3) δ: 7.32 (d, J = 8.2 Hz, 2H), 7.14
(d, J = 8.5 Hz, 2H), 5.37 (d, J = 1.4 Hz, 1H), 5.16 (d, J = 1.1 Hz, 1H),
4.35−4.22 (m, 1H), 4.22−3.96 (m, 2H), 3.05 (ddd, J = 14.4, 4.5, 1.1
Hz, 1H), 2.82 (ddd, J = 14.4, 7.7, 0.9 Hz, 1H), 2.68 (d, J = 6.3 Hz,
1H), 2.34 (s, 3H), 1.28−1.21 (t, J = 7.1 Hz, 3H). HPLC (OJ-H, 95%
hexanes, 5% i-PrOH, 1.0 mL/min, 254 nm): 94% ee, 13.5 min
(major), 18.0 min (minor). The compound had been fully
characterized previously.6a
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Support for this research from the National Science Foundation
(CHE-1212446) is gratefully acknowledged.
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Ethyl (S)-2-Hydroxy-4-m-tolylpent-4-enoate (1e). 72 mg, 61%
yield. 1H NMR (400 MHz, CDCl3) δ: 7.25−7.17 (m, 3H), 7.14−7.06
(m, 1H), 5.38 (d, J = 1.4 Hz, 1H), 5.19 (d, J = 1.1 Hz, 1H), 4.31−4.23
(m, 1H), 4.19−3.99 (m, 2H), 3.05 (ddd, J = 14.4, 4.5, 1.0 Hz, 1H),
2.83 (ddd, J = 14.4, 7.7, 0.9 Hz, 1H), 2.69 (d, J = 6.2 Hz, 1H), 2.36 (s,
3H), 1.24 (t, J = 7.1 Hz, 3H). HPLC (IA, 98% hexanes, 2% i-PrOH,
1.0 mL/min, 254 nm): 87% ee, 15.6 min (minor), 16.3 min (major).
The compound had been fully characterized previously.6a
Ethyl (S)-2-Hydroxy-4-o-tolylpent-4-enoate (1f). 86 mg, 73% yield.
1H NMR (400 MHz, CDCl3) δ: 7.21−7.10 (m, 4H), 5.34 (dd, J = 2.9,
1.3 Hz, 1H), 5.04 (dd, J = 1.8, 0.5 Hz, 1H), 4.19−4.13 (m, 1H), 4.13−
3.93 (m, 2H), 2.90 (dddd, J = 14.4, 4.1, 1.3, 0.7 Hz, 1H), 2.82−2.65
(m, 2H), 2.33 (s, 3H), 1.20 (t, J = 7.1 Hz, 3H). HPLC (OJ-H, 95%
hexanes, 5% i-PrOH, 1.0 mL/min, 254 nm): 89% ee, 9.2 min (major),
10.9 min (minor). The compound had been fully characterized
previously.6a
Ethyl (S)-3-(Cyclopent-1-en-1-yl)-2-hydroxypropanoate (1g). 71
mg, 77% yield. 1H NMR (400 MHz, CDCl3) δ: 5.52 (br s, 1H), 4.35−
4.28 (m, 1H), 4.24 (qd, J = 7.1, 1.2 Hz, 2H), 2.74 (d, J = 5.0 Hz, 1H),
2.61 (dd, J = 15.1, 3.6 Hz, 1H), 2.50 (dd, J = 15.4, 7.4 Hz, 1H), 2.40−
2.18 (m, 4H), 1.88 (p, J = 7.4 Hz, 2H), 1.30 (t, J = 7.1 Hz, 3H). Chiral
HPLC (OD-H, 98% hexanes, 2% i-PrOH, 1.0 mL/min, 210 nm): 87%
ee, 7.8 min (major), 9.2 min (minor). The compound had been fully
characterized previously.6a
REFERENCES
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(1) (a) Mikami, K.; Terada, M. In Comprehensive Asymmetric
Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer:
Berlin, 1999; Vol. III, Chapter 32. (b) Snider, B. B. In Comprehensive
Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford,
U.K., 1991. (c) Mikami, K.; Shimizu, M. Chem. Rev. 1992, 92, 1021.
(d) Mikami, K.; Terada, M.; Narisawa, S.; Nakai, T. Synlett 1992, 255.
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1717. (f) Dias, L. C. Curr. Org. Chem. 2000, 4, 305. (g) Clarke, M. L.;
France, M. B. Tetrahedron 2008, 64, 9003.
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(4) Rueping, M.; Theissmann, T.; Kuenkel, A.; Koenigs, R. M. Angew.
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(5) Maruoka, K.; Hoshino, Y.; Shirasaka, T.; Yamamoto, H.
Tetrahedron Lett. 1988, 29, 3967.
(6) (a) Zhao, J.-F.; Tsui, H.-Y.; Wu, P.-J.; Lu, J.; Loh, T.-P. J. Am.
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H.; Loh, T.-P. Org. Lett. 2009, 11, 5714. (c) Zhao, Y.-J.; Li, B.; Tan, L.-
J. S.; Shen, Z.-L.; Loh, T.-P. J. Am. Chem. Soc. 2010, 132, 10242.
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111, 1940. (b) Mikami, K.; Terada, M.; Nakai, T. J. Am. Chem. Soc.
1990, 112, 3949. (c) Mikami, K.; Matsukawa, S. J. Am. Chem. Soc.
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Vojkovsky, T. J. Am. Chem. Soc. 2000, 122, 7936. (g) Hao, J.; Hatano,
M.; Mikami, K. Org. Lett. 2000, 2, 4059. (h) Kezuka, S.; Ikeno, T.;
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Am. Chem. Soc. 2002, 124, 2882. (j) Ruck, R. T.; Jacobsen, E. N.
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Ethyl (S)-3-(Cyclohex-1-en-1-yl)-2-hydroxypropanoate (1h). 70
1
mg, 71% yield. H NMR (400 MHz, CDCl3) δ: 5.52 (s, 1H), 4.28−
4.18 (m, 3H), 2.67 (d, J = 6.4 Hz, 1H), 2.44 (dd, J = 14.0, 3.9 Hz, 1H),
2.27 (dd, J = 13.9, 8.0 Hz, 1H), 1.99 (m, 4H), 1.64−1.52 (m, 4H),
1.28 (t, J = 7.1 Hz, 3H). Chiral HPLC (IA, 95% hexanes, 5% i-PrOH,
1.0 mL/min, 210 nm): 90% ee, 13.0 min (major), 14.1 min (minor).
The compound had been fully characterized previously.6a
Ethyl (S)-3-(Cyclohept-1-en-1-yl)-2-hydroxypropanoate (1i). 85
1
mg, 80% yield. H NMR (400 MHz, CDCl3) δ: 5.65 (t, J = 6.4 Hz,
1H), 4.24−4.18 (m, 1H), 4.21 (q, J = 7.1 Hz, 2H), 2.62 (d, J = 5.7 Hz,
1H), 2.47 (dd, J = 13.6, 4.5 Hz, 1H), 2.29 (dd, J = 13.6, 7.8 Hz, 1H),
2.16−2.06 (comp, 4H), 1.74−1.69 (comp, 2H), 1.51−1.44 (comp,
4H), 1.29 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ: 174.7,
139.5, 130.8, 69.3, 61.4, 45.3, 32.9, 32.4, 28.4, 27.0, 26.5, 14.2. HPLC
(IA, 95% hexanes, 5% i-PrOH, 1.0 mL/min, 210 nm): 93% ee, 12.1
min (major), 12.9 min (minor). [α]2D3 = −18.6 (c 0.9, CHCl3). HRMS
(ESI+): calcd for C12H21O3 ([M + H]+) 213.1491, found 213.1498.
Ethyl (S,E)-3-(Cyclooct-1-en-1-yl)-2-hydroxypropanoate (1j). 94
1
mg, 83% yield. H NMR (400 MHz, CDCl3) δ: 5.49 (t, J = 8.2 Hz,
1H), 4.30−4.25 (m, 1H), 4.24 (q, J = 7.1 Hz, 2H), 2.60 (d, J = 5.8 Hz,
1H), 2.52 (dd, J = 13.4, 3.4 Hz, 1H), 2.28 (dd, J = 14.4, 8.8 Hz, 1H),
2.19 (m, 2H), 2.13 (comp, 2H), 1.54−1.48 (comp, 8H), 1.30 (t, J =
7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ: 174.7, 135.7, 128.4,
69.2, 61.3, 42.2, 29.7, 28.5, 28.4, 26.4, 26.3, 26.1, 14.1. HPLC (IA, 95%
hexanes, 5% i-PrOH, 1.0 mL/min, 210 nm): 85% ee, 8.1 min (major),
8.7 min (minor). [α]2D3 = −15.9 (c 1.23, CHCl3). HRMS (ESI+): calcd
for C13H23O3 ([M + H]+) 227.1647, found 227.1650.
(10) (a) Doyle, M. P. In Catalytic Asymmetric Synthesis, 2nd ed.;
Ojima, I., Ed.; Wiley-VCH: New York, 2000; Chapter 5.5. (b) Doyle,
M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic
Synthesis with Diazo Compounds: From Cyclopropanes to Ylides; Wiley-
Interscience: New York, 1998. (c) Doyle, M. P.; Timmons, D. In
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dx.doi.org/10.1021/jo5013674 | J. Org. Chem. XXXX, XXX, XXX−XXX