Article

Ring-Closing Metathesis of Ene-Ynamide: Application to the Synthesis of Medium-Sized Cyclic Dienamide

Corresponding Author

Hideaki Wakamatsu

[email protected]

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

Hideaki Wakamatsu, Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan. Fax: (+81) 22-727-0147

Miwako Mori, Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Hokkaido 061-0293, Japan.

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Maiko Sakagami,

Maiko Sakagami

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

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Miyuki Hanata,

Miyuki Hanata

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

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Mitsuhiro Takeshita,

Mitsuhiro Takeshita

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

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Miwako Mori,

Corresponding Author

Miwako Mori

[email protected]

Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Hokkaido 061-0293, Japan

Hideaki Wakamatsu, Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan. Fax: (+81) 22-727-0147

Miwako Mori, Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Hokkaido 061-0293, Japan.

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Hideaki Wakamatsu,

Corresponding Author

Hideaki Wakamatsu

[email protected]

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

Hideaki Wakamatsu, Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan. Fax: (+81) 22-727-0147

Miwako Mori, Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Hokkaido 061-0293, Japan.

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Maiko Sakagami,

Maiko Sakagami

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

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Miyuki Hanata,

Miyuki Hanata

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

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Mitsuhiro Takeshita,

Mitsuhiro Takeshita

Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan

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Miwako Mori,

Corresponding Author

Miwako Mori

[email protected]

Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Hokkaido 061-0293, Japan

Hideaki Wakamatsu, Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan. Fax: (+81) 22-727-0147

Miwako Mori, Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Hokkaido 061-0293, Japan.

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First published: 26 July 2010

https://doi.org/10.1002/masy.200900035

Citations: 16

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Abstract

Summary: Ring-closing metathesis (RCM) of ene-ynamide, which could be applied to the synthesis of various heterocycles containing 7- and 8-membered rings, was investigated. Ene-ynamides are easily synthesized by the known method. When a toluene solution of ene-ynamide was stirred in the presence of a catalytic amount of second-generation ruthenium carbene complex 1 under an ethylene atmosphere, RCM proceeded smoothly to provide a heterocyclic compound having a diene moiety in good to high yield. A substituent of the ynamide moiety affected the yield of the cyclized product.

References

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4 The spectrum data of 2-(p-Toluenesulfonyl)-3-vinyl-2,5-dihydro-1H-benzo[c]azepine (3a): IR (neat) ν 1597 (w), 1338 (s), 1159 (s) cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 2.30 (s, 3H), 3.30 (d, J=5.8Hz, 2H), 4.81 (s, 2H), 5.13 (d, J=10.6Hz, 1H), 5.43 (d, J=16.9Hz, 1H), 5.77 (t, J=5.8Hz, 1H), 6.38 (dd, J=10.6, 16.9Hz, 1H), 6.73 (d, J=7.7Hz, 1H), 6.97 (d, J=8.2Hz, 2H), 7.06 (ddd, J=1.9, 7.3, 7.3Hz, 1H), 7.11-7.19 (m, 2H), 7.27 (d, J=8.2Hz, 2H); ¹³C NMR (100MHz, CDCl₃) δ 21.4, 33.9, 53.5, 115.1, 125.0, 126.3, 127.3, 127.4, 128.8, 129.0, 129.6, 129.8, 135.2, 135.3, 137.0, 141.1, 142.6; EI-LRMS m/z 325 (M⁺), 260, 170, 117, 91; EI-HRMS m/z calcd for C₁₉H₁₉O₂NS (M⁺) 325.1136, found 325.1121.
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5The spectrum data of 1-(p-Toluenesulfonyl)-7-vinyl-2,3,4,5-tetrahydro-1H-azepine (5a): IR (neat) ν 1599 (w), 1343 (s), 1158 (s) cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 1.29-1.36 (m, 2H), 1.66-1.73 (m, 2H), 1.84-1.90 (m, 2H), 2.42 (s, 3H), 3.49 (br, 2H), 5.05 (d, J=10.6Hz, 1H), 5.29 (d, J=17.2Hz, 1H), 5.94 (dd, J=6.8, 7.3Hz, 1H), 6.25 (dd, J=10.6, 17.2Hz, 1H), 7.27 (d, J=8.2Hz, 2H), 7.76 (d, J=8.2Hz, 2H). ¹³C NMR (100MHz, CDCl₃) δ 21.5, 23.6, 26.0, 29.2, 49.1, 114.6, 127.5, 129.4, 131.9, 134.6, 139.1, 142.4, 143.1; EI-LRMS m/z 277 (M⁺), 212, 155, 122, 91; EI-HRMS m/z calcd for C₁₅H₁₉O₂NS (M⁺) 277.1136, found 277.1134.
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6The spectrum data of Ethyl 2-[1,5-Bis-(p-toluenesulfonyl)-4,5-dihydro-1H-benzo[b][1,4]diazepin-2-yl]-acrylate (7b): IR (KBr) ν 1720 (m), 1598 (w), 1355 (s), 1164 (s) cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 1.24 (t, J=7.2Hz, 3H), 2.42 (s, 3H), 2.44 (s, 3H), 3.73 (dd, J=2.9, 18.4Hz, 1H), 4.06-4.15 (m, 2H), 4.57 (dd, J=3.9, 18.4Hz, 1H), 5.30 (dd, J=2.9, 3.9Hz, 1H), 5.88 (s, 1H), 6.25 (s, 1H), 7.26-7.36 (m, 7H), 7.46 (m, 1H), 7.72 (d, J=8.2Hz, 2H), 7.87 (d, J=8.2Hz, 2H); ¹³C NMR (100MHz, CDCl₃) δ 14.1, 21.6, 21.6, 49.1, 61.0, 121.4, 125.7, 127.5, 128.1, 128.3, 128.4, 129.1, 129.5, 129.9, 130.4, 136.3, 136.9, 137.0, 137.8, 139.4, 140.3, 143.7, 144.0, 165.1; EI-LRMS m/z 552 (M⁺), 507, 397, 242, 169, 139, 91; EI-HRMS m/z calcd for C₂₈H₂₈O₆N₂S₂ (M⁺) 552.1389, found 552.1399.
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7The spectrum data of Ethyl 2-[1,5-Bis-(toluene-4-sulfonyl)-1,4,5,6,7,8-hexahydro-[1,5]diazocin-2-yl]-acrylate (11b): IR (neat) ν 1717 (s), 1598 (w), 1343 (s), 1161 (s) cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 1.15 (t, J=7.3Hz, 3H), 1.86-1.93 (m, 2H), 2.40 (s, 3H), 2.44 (s, 3H), 3.41-3.47 (m, 2H), 3.63 (t, J=5.3Hz, 2H), 3.85 (d, J=8.2Hz, 2H), 3.90 (q, J=7.3Hz, 2H), 5.81 (s, 1H), 6.16 (s, 1H), 6.18 (t, J=8.2Hz, 1H), 7.23 (d, J=7.7Hz, 2H), 7.31 (d, J=7.7Hz, 2H), 7.58 (d, J=8.2Hz, 2H), 7.65 (d, J=8.2Hz, 2H); ¹³C NMR (100MHz, CDCl₃) δ 13.9, 21.5, 21.5, 27.9, 44.1, 48.5, 51.8, 60.9, 127.0, 127.4, 129.4, 129.8, 130.5, 131.0, 136.2, 136.7, 137.8, 139.3, 143.4, 143.4, 165.0; EI-LRMS m/z 518 (M⁺), 473, 397, 363, 335, 317, 267, 238, 207, 180, 155, 134, 91; EI-HRMS m/z calcd for C₂₅H₃₀O₆N₂S₂ (M⁺) 518.1545, found 518.1538.
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Volume293, Issue1

Special Issue:Olefin Metathesis

July 2010

Pages 5-9

Ring-Closing Metathesis of Ene-Ynamide: Application to the Synthesis of Medium-Sized Cyclic Dienamide

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Ring-Closing Metathesis of Ene-Ynamide: Application to the Synthesis of Medium-Sized Cyclic Dienamide

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