Heteromacrocycles from Ring-Closing Metathesis of Unsaturated Furanic Ethers

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Heteromacrocycles from Ring-Closing Metathesis ofUnsaturated Furanic EthersLouis Cottier a , Gérard Descotes a & Yaya Soro aa Université Claude-Bernard Lyon I, Laboratoire de Chimie Organique II, UMR CNRS-Université N° 5622, ESCPE-Lyon, Villeurbanne, FrancePublished online: 21 Aug 2006.

To cite this article: Louis Cottier , Gérard Descotes & Yaya Soro (2003): Heteromacrocycles from Ring-Closing Metathesisof Unsaturated Furanic Ethers, Synthetic Communications: An International Journal for Rapid Communication of SyntheticOrganic Chemistry, 33:24, 4285-4295

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MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016

SYNTHETIC COMMUNICATIONS�

Vol. 33, No. 24, pp. 4285–4295, 2003

Heteromacrocycles from Ring-Closing

Metathesis of Unsaturated Furanic Ethers

Louis Cottier,* Gerard Descotes, and Yaya Soro

Universite Claude-Bernard Lyon I,

Laboratoire de Chimie Organique II,

UMR CNRS-Universite N� 5622, ESCPE-Lyon,

Villeurbanne, France

ABSTRACT

New 2,5-bis(unsaturated alkyloxymethyl)-furan led to macrocyclic

furanic derivatives in the presence of Grubb’s catalyst via dimeri-

zation or direct intramolecular metathesis according to the length

of the sidearm.

Key Words: Oxygen heterocycles; Ring-closing metathesis; Macro-

cycles.

*Correspondence: Louis Cottier, Universite Claude-Bernard Lyon I,

Laboratoire de Chimie Organique II, UMR CNRS-Universite N� 5622,

ESCPE-Lyon, Bat. 308, 43, Blvd. du 11 Novembre 1918, 69622 Villeurbanne,

France; Fax: (33)4 72 44 81 60; E-mail: [email protected].

4285

DOI: 10.1081/SCC-120026858 0039-7911 (Print); 1532-2432 (Online)

Copyright & 2003 by Marcel Dekker, Inc. www.dekker.com

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INTRODUCTION

As part of project to develop the use of the 5-hydroxymethylfurfural(HMF)[1] 1, issued from the acid catalyzed dehydration of fructoseor inulin,[2] we thought to transform the HMF 1 to unsaturatedmacrocycle polyether compounds containing furan subcyclic unit. Suchheteromacrocycles with a number of structure limited due to thepresence of carbon–carbon double bonds should presented complexationproperties[3] and alkali metal cation–p interactions.[4] These heteromacro-cyclic substrates could be easily prepared from unsaturated molecules viathe ring closing metathesis (RCM) catalyzed by carbene transitioncomplexes (Mo, Ru).[5] The cyclization of allylic ethers or unsaturatedamines to the corresponding five, six or seven membered oxa or azacycleshas been demonstrated.[5b,5d,6] Very recently Tae and Yang[7] describedthe olefin metathesis macrocyclization of p-bis[(allyl or 4-penten-1-yloxy)methyl]benzene leading to mono, di, or trimeric products.

In this article we report the syntheses of heteromacrocycles 6 and 9

via the ring closing metathesis (RCM) of 2,5-disubstituted furans 3a

and 3b catalyzed by commercially available Grubbs’ catalyst.[5b,6b]

Until now, some publications mentioned the metathesis of compoundscontaining furanic moiety using tungsten alkylidene complexe,[8] molyb-denum,[9] or ruthenium[10] catalysts but nobody applied RCM to2,5-unsaturated disubstituted furans. We used the benzylidene-bis(tricyclohexylphosphine) ruthenium dichloride 4 (Grubbs’ catalyst)because of its good properties (high reactivity, stability to air and varioussolvent, remarkable functional group tolerance).

RESULTS AND DISCUSSION

The 2,5-unsaturated disubstituted furans 3a and 3b were preparedaccording to the Williamson reaction between the 2,5-bis (hydroxy-methyl)-furan 2 issued from hydroxymethylfurfural (HMF)[1b] 1 andthe appropriate bromide. The best yield in 3a was obtained usingsodium hydride in presence of tetrabutylammonium iodide (TBAI) anda mixture of THF and DMSO as solvent. The bis ether 3b wasprepared in 71% yield as described for 2a. This yield was increased upto 95% under liquid liquid phase transfer. Unfortunately we were notable to obtain the butenyl ether from 2 and the 4-bromobut-1-enebecause, in the basic conditions, a,b-elimination reaction yieldingbutadiene competes with the slower substitution reaction. It must be

4286 Cottier, Descotes, and Soro

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noticed that Tae and Yang[7]did not prepare the p-bis[(3-buten-1-yloxy)-methyl]benzene but the lower or upper homologues. (Sch. 1)

The ring closure of furanic compounds 3 in presence of benzylideneruthenium complex 4 was realized under high dilution to avoid an easycross metathesis polymerization which occurred with a concentration lessthan 0.04mol/L. The observed results of different attempts are summa-rized in the Table 1. The formation of 6 (ZZ and EE) instead of 5 isprobably due to the conformational constraints in the original substrate

Scheme 1.

Unsaturated Furanic Ethers 4287

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and in the eventual product 5. The activation with ultrasound did notincrease the rate or the yield.

It must be pointed out that De Armas et al.[10b] did not observe sucha dimerization during the ring closing metathesis of 7-(4-pentenyl)-L-arabino-hept-1-enitol derivative A. They reported the formation of amedium sized bridged oxabicyclo[6.2.1] alkene B while Tae and Yang[7]

described the formation of a dimeric substrate from the p-bis[(allyloxy)-methyl]benzene with the same catalyst 4. (Sch. 2)

The structure of macrocycles 6 was established according to themass spectra data because the NMR spectra could agreed with a bicycliccompound 5 or a bis furanic macrocycle 6. Fortunately, the FAB massspectra showed a molecular ion peak at m/z equal to 361 [MþH]þ or to383 [MþNa]þ proving the dimeric structure of 6. Due to the presence of,at least, a plane of symmetry, the 1H and 13CNMR spectra, showedonly one signal for each of protons 4-H, 6-H, 7-H and 8-H and for

Table 1. Ring-closing metathesis of compounds 3a and 3b with Grubbs’

catalyst 4.

Substratea

(amount in mmol)

Catalyst 5

mol% Time (h)

Products

(Yield [%]) Isomers, [%]

3a (1)b 2.5 18 6 (26) ZZ/EE, 70/30

3a (1)c 2.5 18 6 (63) ZZ/EE, 74/26

3a (1)c,d 2.5 4.5 6 (48) ZZ/EE, 78/22

3a (1)c 10 18 6 (51) ZZ/EE, 70/30

3b (0.5)c 10 4 9 (96) Z/E, 61/39e

aIn dichloromethane at reflux.bConcentration in mol/L:0.02.cConcentration in mol/L:0.005.dUnder sonication.eThe ratio could be inverted.

Scheme 2.


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each of carbons C-4, C-5, C-6, C-7, and C-8. An attempt to obtain thecompound 5 with the configuration Z from the chloro alcohol 8 (Sch. 3)did not give the compound 5 but led to the macrocycle 6. This resultallows to specify the stereochemistry Z, Z and E, E of the obtainedisomers 6. The restricted number of the signals in 13CNMR excludedthe formation of the Z,E stereoisomer (Sch. 3).

In the case of the furanic ether 3b with longer sidechains, the RCMgave the monomeric bicyclic compound 9 with an excellent yield (96%) asa mixture of stereoisomers Z/E in a ratio 3/2 or 2/3. The bicyclic structurewas established according to NMR and mass spectra. As the compounds9 have elements of symmetry, the configuration Z or E of each isomercould not be attributed from NMR. Unfortunately we have not be ableto get a single crystal of the major isomer 9, which is solid, to establishthe structure with an X-ray analysis

CONCLUSION

The HMF, issued from the acid catalyzed dehydration of fructose orinulin, can easily lead to 2,5-unsaturated diethers via the 2,5- bis(hydroxy-methyl)-furan. The RCM reaction of these ethers were carried out inpresence of commercial and stable Grubbs’ catalyst with good yields.The structure of the macrocyclic unsaturated polyethers depends on thelength of the sidearms. If, on both sidearms, there are three atomsbetween the carbon–carbon double bond and the furan moiety, acyclodimerization was observed leading to a heteromacrocycle with two

Scheme 3.


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furan subcyclic units. The allylic ether 3a underwent probably a crossmetathesis followed by a RCM leading to the macrocycle 6 and not to themonofuranic compound 5. But if the sidearms are longer, an unsaturatedmacrocyclic polyether containing one furan subcyclic unit was achieved.The bis pentenyl ether 3b gave the bicyclic product 9 through a directintramolecular metathesis. These syntheses could be applied to makelarger unsaturated heteromacrocycles.

EXPERIMENTAL SECTION

General Remarks. Melting point were uncorrected. Proton NMRspectra[11] at 200MHz and 13CNMR spectra[11] at 50MHz were recordedby using a Bruker spectrometer AC 200. Mass spectra were measuredwith a Finnigan MAT 95 XL spectrometer. Column chromatographywas performed using Geduran Si 60 silica gel (E. Merck). The ratios ofsolvents were measured in volume. Grubb’s catalyst 4 was purchasedfrom Aldrich.

2,5-bis-Hydroxymethyl-furan (2). To 5-hydroxymethylfurfural(12.3 g, 97.5mmol) dissolved in dry methanol (100mL) and maintainedat 4�C was added slowly sodium borohydride (7.5 g, 198.3mmol). Thereaction was stirred at room temperature for 15min. Then the methanolwas evaporated under vacuum and water was added to the residue. Thisnew mixture was neutralized by addition of HCl (2N) and then extractedwith ethyl acetate (7� 40mL). The organic phase was dried (MgSO4) andconcentrated. The raw product was chromatographed (dichloromethane/ethyl acetate, 10:1) to give 2 (12.1 g, 97%). White solid. Rf¼ 0.38(dichloromethane/ethyl acetate, 10:1). M.p.: 75�C. Lit.[12] M.p. 74–75�C;1H and 13CNMR data were in agreement with those reported in theliterature;[12] 1HNMR (200MHz, [d6] DMSO): �¼ 6.2 (s, 1H, 3-H), 5.1(t, 1H, OH), 4.3 (d, 2H, J6a,6b¼ 5.6, 6-Ha, 6-Hb). 13CNMR (50MHz, [d6]DMSO): �¼ 154.8 (C-2), 107.6 (C-3), 55.9 (C-6).

2,5-bis-Allyloxymethyl-furan (3a). Into a suspension of HNa (0.2 g,8.3mmol) in THF (4mL) was dropped a solution of 2 (0.32 g, 2.5mmol)in dry DMSO (2mL). The mixture was stirred at room temperature for30 min and then was heated at 40�C before adding tetrabutylammoniumiodide (0.15 g, 0.4mmol) and allyl bromide (1.2 g, 10mmol). The reactionwas monitored by TLC (petroleum ether/ethyl acetate, 1:1). The reactionwas stirred for 18 h until the alcohol 2 had been converted. Then diethylether (4mL) and water (5mL) were added and the solution was extractedwith diethyl ether (5� 15mL). The combined organic layers were dried(MgSO4) and concentrated. The crude product was chromatographed


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(petroleum ether/ethyl acetate, 5/1 200mL and then 1/1) to give 3a (0.4 g,77%). Colorless oil. Rf ¼ 0.38 (petroleum ether/ethyl acetate,5/1); 1HNMR (200MHz, CDCl3): �¼ 6.23 (s, 2H, 4-H), 5.92 (ddt,2H, J8,7¼ 5.6Hz, J8,9b¼ 10.3Hz, J8,9a¼ 17.2Hz, 8-H), 5.27 (dq, 2H,J9a,7¼ J9a, J9b¼ 1.5Hz, J9a,8¼ 17.2Hz, 9a-H), 5.24 (dq, 2H,J9b,9a¼ J9b,7¼ 1.5Hz, J9b,8¼ 10.3Hz, 9b-H), 4.44 (s, 4H, 6-H), 4.03 (dt,4H, J7,9b¼ J7,9a¼ 1.5Hz, J7,8¼ 5.6Hz, 7-H). 13CNMR (50MHz,CDCl3): �¼ 152.1 (C-5), 134.5 (C-8), 117.5 (C-9), 110.0 (C-4), 71.0(C-7), 64.0 (C-6); MS (CI isobutane) C12H16O3 (M:208): m/z¼ 209[MþH]þ. Anal. calcd. for C12H16O3: C, 69.20; H, 7.74. Found:C, 68.87; H, 7.66.

2,5-bis-Pent-4-enyloxymethyl-furan (3b). The compound 3b wasobtained according to the same procedure with a yield of 71% but thefollowing procedure gave a better yield—A mixture of diol 2 (130mg,1mmol), 5-bromo-1-pentene (447mg, 3mmol), aliquat 336 (81mg,0.2mmol) and KOH (9.4N, 0.3mL) was stirred at 85�C. The reactionwas monitored by TLC (petroleum ether/ethyl acetate, 5:1). After 24 h,the reaction mixture was filtered and concentrated. The residue waschromatographed (petroleum ether/ethyl acetate, 5:1) to give 3b

(251mg, 0.95mmol, 95%). Light yellow oil. Rf¼ 0.46 (petroleum ether/-ethyl acetate); 1HNMR (200MHz, CDCl3): �¼ 6.26 (s, 2H, 4-H), 5.81(m, 2H, J10,9¼ 6.6Hz, J10,11b¼ 10.2Hz, J10,11a¼ 17Hz, J10,8¼ 6.7Hz, 10-H), 5.05 (dq, 2H, J11a,11b¼ 1.9Hz, J11a,10¼ 17Hz, J11a,9¼ 1.2Hz, 11a-H),4.94 (dq, 2H, J11b,11a¼ 1.9Hz, J11b,10¼ 10.2Hz, J11b,9¼ 1Hz, 11b-H),4.43 (s, 4H, 6-H), 3.49 (t, 4H, J7,8¼ 6.6Hz, 7-H), 2.11 (m, 4H,J8,77¼ 6.6Hz, J8,9¼ 6.8Hz, J8,10¼ 7Hz, 8-H), 1.7 (m, 4H, J9,8¼ 6.8Hz,J9,10¼ 6.6Hz, J9,11 Hz¼ 1Hz, J9,11a¼ 1.2Hz, 9-H); 13CNMR (50MHz,CDCl3): �¼ 152.3 (C-5), 138.2 (C-10), 114.8 (C-11), 109.7 (C-3), 69.6(C-7), 64.9 (C-6), 30.3 (C-8), 28.8 (C-9); MS (CI isobutane) C16H24O3

(M:264): m/z¼ 265 [MþH]þ. Anal. calcd. for C16H24O3: C, 72.69;H, 9.15. Found: C, 72.51; H, 9.04.

3,8,15,20,25,26-Hexaoxa-Tricyclo[20.2.1.110,13] hexacosa-1(24),5,10,

12,17,22-hexaene (6 ZZ and EE). A. from allyloxymethyl-furan 3a.—Asolution of Grubbs’ catalyst 4 (20.6mg, 0.025mmol) in dry and degasseddichloromethane (20mL) was added by syringe into a flask containingthe furanic compound 3a (208mg, 1mmol) dissolved in dry and degasseddichloromethane (180mL). The mixture, heated at 40�C, was stirred for18 h. The reaction was monitored by TLC (dichloromethane/acetone,5:0.2). The reaction mixture was concentrated. The residue was chroma-tographed (dichloromethane/acetone, 5:0.2) to give 6 (227mg,0.63mmol) as a mixture of diastereoisomers. Each isomer was separatedwith a second chromatography (petroleum ether/ethyl acetate, 1:2) giving


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the isomer 6 ZZ (148mg, 46.6%) and the isomer 6 EE (59mg, 16.4%);the ratio of the stereoisomers ZZ/EE was equal to 74/26.

B. from chloro-alcohol 8.—Into a suspension of HNa (10mg,0.4mmol) and TBAI (12mg, 0.03mmmol) in THF (2.5mL) was droppeda solution of 8 (40mg, 0.2mmol) in dry DMSO (1.5mL). The mixturewas stirred at room temperature for 24 h. After the work-up such as 3a,the crude product was chromatographed (petroleum ether/ethyl acetate,1:2) to give 6 ZZ (26mg, 0.07mmol, 72%).

Compound 6 (5Z, 17Z). White powder. Rf¼ 0.66 (petroleum ether/ethyl acetate, 1:2). M.p.: 92�C. 1HNMR (200MHz, CDCl3): �¼ 6.26 (s,4H, 4-H), 5.74 (t, 4H, J8,7a¼ J8,7b¼ 4.9Hz, 8-H), 4.41 (s, 8H, 6-H), 4.06(t, 8H, J7a,8¼ J7b,8¼ 4.9Hz, 7-H). 13CNMR (50MHz, CDCl3): �¼ 152.3(C-5), 129.6 (C-8), 110.0 (C-4), 69.6 (C-7), 63.7 (C-6). HRMS calcd. forC20H25O6 [MþH]þ: 361.1651. Found: 361.1648.

Compound 6 (5E, 17E). White powder. Rf¼ 0.77 (petroleum ether/ethyl acetate, 1:2). M.p.: 89–90�C. 1HNMR (200MHz, CDCl3): �¼ 6.26(s, 4H, 4-H), 5.82 (dd, 4H, J8,7a¼ 1.3Hz, J8,7b¼ 2.9Hz, 8-H), 4.44 (s, 8H,6-H), 4.01 (d, 4H, J7a,8¼ 1.3Hz, 7a-H), 4.02 (d, 4H, J7b–8¼ 2.9Hz,7b-H). 13CNMR (50MHz, CDCl3): �¼ 152.1 (C-5), 129.8 (C-8), 110.3(C-4), 64.7 (C-7), 63.7 (C-6). HRMS calcd. for C20H25O6 [MþH]þ:361.1651. Found: 361.1649.

(2Z)-5-(4-Chlorobut-2-enyloxymethyl-furan)-2-carbaldehyde (7). Intoa suspension of HNa (190mg, 7.9mmol) in THF (8mL) was added thehydroxymethylfurfural 1 (500mg, 3.96mmol), (2Z)-1,4-dichloro-but-2-ene (4.1mL, 39mmol) and TBAI (235mg). The mixture washeated at 40�C for 24 h. The reaction mixture was concentrated andchromatographed (petroleum ether/ethyl acetate, 2:3) to give 7 (132mg,13%). Yellow oil. Rf¼ 0.8 (petroleum ether/ethyl acetate, 2:3). 1HNMR(200MHz, CDCl3): �¼ 9.63 (s, 1H, CHO), 7.23 (d, 1H, J3,4¼ 3.55Hz,3-H), 6.56 (d, 1H, J4,3¼ 3.55Hz, 4-H), 5.77 (m, 2H, 8-H and 9-H), 4.44(s, 2H, 6-H), 4.12 (m, 4H, 7-H and 10-H). 13CNMR (50MHz, CDCl3):�¼ 177.7 (CHO), 158.0 (C-5), 157.7 (C-2), 129.9 (C-9), 129.1 (C-8), 122.0(C-3), 111.5 (C-4), 65.7 (C-7), 64.2 (C-6), 39.0 (C-10). HRMS calcd. forC10H12O3Cl [MþH]þ: 215.0475. Found: 215.0476.

(2Z)-[5-(4-Chlorobut-2-enyloxymethyl)-furan-2-yl]-methanol (8). Thecompound 8 was obtained according to the procedure of compound 1.The aldehyde 7 (100mg, 0.46mmol) with NaBH4 (35mg, 0.9mmol in drymethanol (4mL) gave after usual work-up and chromatography (petro-leum ether/ethyl acetate, 2:3) the alcohol 8 (45.7mg, 0.21mmol, 46%).Colorless oil. Rf¼ 0.35 (petroleum ether/ethyl acetate, 2:3). 1HNMR(200MHz, CDCl3): �¼ 6.3 (d, 1H, J3,4¼ 3.2Hz, 3-H), 6.25 (d, 1H,J4,3¼ 3.2Hz, 4-H), 5.77 (m, 2H, 8-H and 9-H), 4.59 (s, 2H, 11-H), 4.44


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(s, 2H, 6-H), 4.12 (m, 4H, 7-H and 10-H). 13CNMR (50MHz, CDCl3):�¼ 154.8 (C-5), 151.2 (C-2), 130.3 (C-9), 128.8 (C-8), 110.5 (C-3), 108.4(C-4), 64.9 (C-7), 64.1 (C-6), 57.3 (C-11), 39.1 (C-10). HRMSC10H13O3Cl [M]þ: 216.0553. Found: 216.0550.

3,8,15,20,25,26-Hexaoxa-tricyclo[20.2.1.110, 13

] hexacosa-1(24),5,10,12,

17,22-hexaene (9 Z/E or E/Z). A solution of Grubb’s catalyst 4 (41mg,0.05mmol) in dry and degassed dichloromethane (10mL) was added bysyringe into a flask containing 3b (132mg, 0.5mmol) dissolved intodichloromethane (90mL). The mixture, heated at 40�C, was stirred for4 h. Then the solvent was evaporated and the residue was chromato-graphed (petroleum ether/ethyl acetate, 1:1) to give 9 (113mg,0.48mmol, 96%) as a mixture of isomers in a ratio 61/39. These isomerswere separated with a second chromatography (petroleum ether/ethylacetate, 5:0.5) providing a minor product (44mg, 0.18mmol) and amajor product (69mg, 0.29mmol)

Minor product 9. Colorless oil. Rf¼ 0.23 (petroleum ether/ethylacetate, 5:0.5). 1HNMR (200MHz, CDCl3): �¼ 6.23 (s, 2H, 4-H), 5.19(dd, 2H, J10,9a¼ 4.4Hz, J10,9b¼ 5.3Hz, 10-H), 4.44 (s, 4H, 6-H), 3.41 (t,4H, J7a,8a¼ J7a,8b¼ J7b,8a¼ J7b,8b¼ 7.2Hz, 7-H), 2.02 (m, 4H, 8-H), 1.53(m, 4H, 9-H). 13CNMR (50MHz, CDCl3): �¼ 153.1 (C-5), 129.1 (C-10),110.2 (C-4), 68.(C-7), 64.3 (C-6), 28.1 (C-8), 27.9 (C-9). MS C14H20O3

(M:236): m/z¼ 236 [M]þ.Major product 9.White powder.Rf¼ 0.26 (petroleum ether/ethyl acet-

ate, 5:0.5). M.p.: 37�C. 1HNMR (200MHz, CDCl3): �¼ 6.29 (s, 2H, 4-H),5.24 (dd, 2H, J10,9a¼ 2.2Hz, J10,9b¼ 5.3Hz, 10-H), 4.47 (s, 4H, 6-H), 3.38(t, 4H, J7a,8a¼ J7a,8b¼ J7b,8a¼ J7b,8b¼ 7Hz, 7-H), 2.03 (m, 4H, 8-H), 1.65(m, 4H, 9-H). 13CNMR (50MHz, CDCl3): �¼ 152.1 (C-5), 130.5 (C-10),110.5 (C-4), 67.4.(C-7), 64 (C-6), 28.3 (C-8), 28 (C-9). MS C14H20O3

(M:236): m/z¼ 236 [M]þ; Anal. calcd. for C14H20O3 (9minorþ 9 major):C, 71.16; H, 8.53. Found: C, 70.89; H, 8.43.

ACKNOWLEDGMENTS

The participation of Sudzucker AG (Mannheim, Germany) inproviding HMF is gratefully acknowedged.

REFERENCES

1. (a) Cottier, L.; Descotes, G.; Eymard, L.; Rapp, K. Synthesesof g-oxo acids or g-oxo esters by photooxygenation of furanic


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2. (a) Cottier, L.; Descotes, G.; Neyret, C.; Nigay, H. New process forthe preparation of 5-hydroxymethylfurfural by thermal degradationof saccharides. Fr. 2,664,273, Jan 1992; Chem. Abstr. 1992, 117,48323u; (b) Lichtenthaler, F.W. (Ed.), Carbohydrates as OrganicRaw Materials; VCH Publ: Weinheim/New York, 1991; 367 pp.

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Received in the UK July 24, 2003


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Heteromacrocycles from Ring-Closing Metathesis of Unsaturated Furanic Ethers

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Transcript of Heteromacrocycles from Ring-Closing Metathesis of Unsaturated Furanic Ethers