Novel Approach Towards the Bicyclic Moiety of Miharamycin, Employing Ring Closure Metathesis

Mélanie Etheve-Quelquejeu; Juan Xie; Jean-Marc Valéry

doi:10.1055/s-2004-820055

LETTER

Novel Approach Towards the Bicyclic Moiety of Miharamycin, Employing Ring Closure Metathesis

Mélanie Etheve-Quelquejeu*, Juan Xie, Jean-Marc Valéry
Synthèse, structure et fonction de molécules Bioactives-CNRS UMR 7613-Equipe ‘Chimie des Glucides’, Université Pierre et Marie Curie, 4 place Jussieu, case 179, 75252 Paris, Cedex 05, France
Fax: +33(1)44275513; e-Mail: quelque@ccr.jussieu.fr;

Abstract

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Abstract

The ring closing metathesis has been successfully used in the construction of the bicyclic moiety of miharamycin from 2-O-allyl-3-C-methylene sugar.

Key words

carbohydrates - ring closure metathesis - bicyclic - annulation

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Referenzen

References

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Spectral data for 3: ¹H NMR (250 MHz, CDCl₃): δ = 3.43 (s, 3 H, OCH₃), 3.75 (m, 2 H, H-5, H-6), 3.95 (m, 2 H, H-2, CH₂), 4.28 (m, 2 H, H-6′, CH₂), 4.83 (d, 1 H, H-1, J = 3.8 Hz), 5.27 (m, 2 H, CH₂=), 5.60 (s, 1 H, CH), 5.95 (m, 1 H, CH=), 7.35 (m, 3 H, Ph), 7.53 (m, 2 H, Ph). ¹³C NMR (63 MHz, CDCl₃): δ = 55.7 (OCH₃), 66.0 (C5), 69.8 (C6), 72.0 (CH₂), 77.0 (C2), 79.0 (C4), 100.0 (C1), 101.9 (CH), 105.4 (CH₂=), 118.3 (CH₂=), 126.7, 128.7, 129.5 (Ph), 134.8 (CH=). [α]_D ²⁰ +70 (c 1, CH₂Cl₂). MS (NH₃, DCI): 336 [M + 18]⁺.

Spectral data for 7: ¹H NMR (250 MHz, CDCl₃): δ = 3.44 (s, 6 H, OCH₃), 3.73 (m, 4 H, H-5, H-6), 3.95 (m, 4 H, H-2, H-4), 4.26 (m, 4 H, CH₂), 4.29 (m, 2 H, H-6), 4.85 (d, 2 H, H-1, J = 3.8 Hz), 5.26 (dd, 4 H, CH₂=), 5.60 (s, 2 H, CH), 5.88 (m, 2 H, CH=), 7.39 (m, 6 H, Ph), 7.54 (m, 4 H, Ph). ¹³C NMR (63 MHz, CDCl₃): δ = 55.7 (OCH₃), 66.0 (C5), 69.8 (C6), 70.8 (CH₂), 77.3 (C2), 78.9 (C4), 99.9 (C1), 101.8 (CH), 105.5 (CH₂=), 126.6, 128.6, 129.5, 130 (Ph), 134.8 (CH=), 139.5 (C_ipso).; MS (NH₃, DCI): 626 [M + 18]⁺.

<A NAME="RG34403ST-14">14</A> Guerra J. Synlett 2003, 423

Spectral data for 8: ¹H NMR (250 MHz, CDCl₃): δ = 2.06 (s, 3 H, OAc) 2.15 (s, 3 H, OAc), 3.40 (s, 3 H, OCH₃), 3.85 (m, 1 H, H-5), 3.98-4.14 (m, 4 H, H-2, H-6, H-7, H-7′), 4.29 (m, 1 H, H-6), 4.81 (d, 1 H, H-1, J = 3.7 Hz), 4.97 (br s, 1 H, H-4), 5.20 (m, 4 H, CH₂=), 5.88 (m, 1 H, CH=). ¹³C NMR (63 MHz, CDCl₃): δ = 21.0. 21.1 (CH₃), 55.7 (OCH₃), 62.9 (C6), 69.6 (C5), 70.0 (C2), 72.0 (C7), 76.8 (C4), 99.1 (C1), 106.5 (CH₂=), 134.5 (CH=), 139.2 (C3), 171.1, 169.8 (CO). Optical rotation: [α]_D ²⁰ +66 (c 1, CH₂Cl₂). MS (NH₃, DCI): 332 [M + 18]⁺.

<A NAME="RG34403ST-16">16</A> Paquette LA. Schloss JD. Efremov I. Fabris F. Gallo F. Mendez-Andino J. Yang J. Org. Lett. 2000, 2: 1259

Spectal data for 9: ¹H NMR (250 MHz, CDCl₃): δ = 2.09 (s, 3 H, OAc) 2.14 (s, 3 H, OAc), 3.42 (s, 3 H, OCH₃), 3.81 (m, 1 H, H-5), 4.18 (m, 2 H, H-6), 4.73 (m, 1 H, H-2), 4.83 (m, 3 H, H-1, CH₂), 5.42 (dd, 1 H, H-4, J = 2.2 Hz, J = 9.7 Hz), 5.60 (bs, 1 H, CH=). ¹³C NMR (63 MHz, CDCl₃): δ = 21.0. 21.1 (CH₃), 55.8 (OCH₃), 62.8 (C6), 67.7 (C4), 68.9 (C5), 77.7 (C7), 83.7 (C2), 99.7 (C1), 119.2 (CH=), 133.5 (C3), 171.1, 169.9 (CO). [α]_D ²⁰ +204 (c 1, CH₂Cl₂). MS (NH₃, DCI): 304 [M + 18]⁺.

Spectral data for 10: ¹H NMR (250 MHz, CDCl₃): δ = 1.6 (br s, 1 H, OH), 2.09 (s, 3 H, OAc) 2.12 (s, 3 H, OAc), 3.39 (s, 3 H, OCH₃), 3.60 (dd, 1 H, H-7), 3.92 (m, 1 H, H-5), 4.10 (d, 1 H, H-2, J = 5.0 Hz), 4.27 (m, 3 H, H-6, H-7′), 4.48 (br s, 1 H, OH), 4.62 (m, 1 H, H-8), 4.73 (d, 1 H, H-1, J = 5.3 Hz), 4.98 (d, 1 H, H-4, J = 10.5 Hz). ¹³C NMR (63 MHz, CDCl₃): δ = 21.1, 21.1 (CH₃), 56.1 (OCH₃), 62.9 (C6), 64.7 (C5), 72.7 (C8), 74 (C7), 74.3 (C4), 78.1 (C3), 83.6 (C2), 98.8 (C1), 173.2, 171.1 (CO). [α]_D ²⁰ +108 (c 1, CH₂Cl₂).

<A NAME="RG34403ST-19">19</A> Paquette LA. Hartung RE. France DJ. Org. Lett. 2003, 6: 869

Spectral data for 11: ¹H NMR (250 MHz, CDCl₃): δ = 2.06 (s, 3 H, OAc) 2.11 (s, 3 H, OAc), 3.37 (s, 3 H, OCH₃), 3.82 (m, 1 H, H-5), 3.97-4.12 (m, 3 H, H-6, H-7), 4.36 (d, 1 H, H-2, J = 5.3 Hz), 4.54 (dd, 1 H, H-7′, J = 5.8 Hz, J = 10.0 Hz), 4.89 (d, 1 H, H-1, J = 5.3 Hz), 5.25 (dd, 1 H, H-8, J = 6.0 Hz, J = 1.8 Hz), 5.42 (d, 1 H, H-4, J = 10.5 Hz). ¹³C NMR (63 MHz, CDCl₃): δ = 20.5, 20.2 (CH₃), 55.4 (OCH₃), 61.8 (C6), 64.1 (C5), 67.4 (C4), 75.4 (C7), 79.3 (C2), 80.4 (C8), 98.9 (C1), 153.0 (CO), 168.7, 170.4 (CO). [α]_D ²⁰ +67 (c 1.2, CH₂Cl₂). MS (NH₃, DCI): 364 [M + 18]⁺. IR 1817, 1750 cm^-1 (CO).

<A NAME="RG34403ST-21">21</A> Anelli PL. Biffi C. Montanari F. Quici S. J. Org. Chem. 1987, 52: 2559

Spectral data for 12: ¹H NMR (250 MHz, CDCl₃): δ = 2.10 (s, 3 H, OAc) 2.19 (s, 3 H, OAc), 3.40 (s, 3 H, OCH₃), 4.00 (m, 1 H, H-5), 4.18-4.30 (m, 5 H, H-2, H-6, H-6′, H-7, H-7′), 4.88 (d, 1 H, H-1, J = 5.5 Hz), 4.92 (br s, 1 H, H-4). ¹³C NMR (63 MHz, CDCl₃): δ = 21.4 (CH₃), 56.3 (OCH₃), 63.0 (C6), 66.0 (C5), 70.6 (C7), 72.5 (C3), 76.6 (C4), 82.0 (C2), 99.1 (C1), 171.3, 175.0 (CO), 207.7 (CO). [α]_D ²⁰ +17 (c 0.3, CH₂Cl₂). MS (NH₃, DCI): 336 [M + 18]⁺.

The crystal struture has been deposited at the Cambridge Crystallographic Center and allocated the deposition number: CCDC 224358.

Spectral data for 13: ¹H NMR (250 MHz, CDCl₃): δ = 2.11 (s, 3 H, OAc), 2.53 (s, 1 H, OH), 2.95 (s, 1 H, OH), 3.52 (s, 3 H, OCH₃), 3.82 (m, 2 H, H-4, H-5), 3.89 (d, 1 H, H-7, J = 10.3 Hz), 4.02 (d, 1 H, H-2, J = 5.5 Hz), 4.18 (dd, 1 H, H-8, J = 4.8 Hz, J = 12.2 Hz), 4.36 (m, 3 H, 2 H-6, H-7′), 4.53 (d, 1 H, OH, J = 12.2 Hz), 4.86 (d, 1 H, H-1, J = 5.3 Hz). MS (NH₃, DCI): 296 [M + 18]⁺.