аЯрЁБс>ўџ <>ўџџџ;џџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџьЅС9 №Пњ&bjbj§Я§Я "BŸЅŸЅ\џџџџџџlBBBBBBBVТТТТоVэ bўўўўўўўўм о о о о о о $O o. ЅBўўўўў ъBBўўЇ ъъъўЪBўBўм ъўм ъцъа BBа ўђ @Щ8G>?РVlТШа а Н 0э а Ш"а ъVVBBBBйPolymer-supported bis(oxazoline)-copper complexes as catalysts in cyclopropanation reactions M. Isabel Burguete,† Josщ M. Fraile,‡ Josщ I. Garcэa,‡ Eduardo Garcэa-Verdugo,† Santiago V. Luis†* and Josщ A. Mayoral‡* †Departamento de Quэmica Inorgсnica y Orgсnica, E.S.T.C.E., Universidad Jaume I, E-12080 Castellѓn and ‡Departamento de Quэmica Orgсnica, Instituto de Ciencia de Materiales de Aragѓn, Facultad de Ciencias, Universidad de Zaragoza-C.S.I.C., E-50009 Zaragoza (Spain) Supporting Information General preparation of bis(oxazoline) ligands Synthesis of 2 and 4: Methyl lithium (2 mmol) was added to a solution of the corresponding bis(oxazoline) 1 (1 mmol) in anhydrous THF at -55КC under Ar atmosphere, and the resulting solution was stirred for 1 h. Then 2 mmol of the alkylating agent (benzyl chloride for 2 or p-vinylbenzyl chloride for 4) were added dropwise and the reaction was heated under reflux for 4 h. The reaction mixture was washed with saturated NH4Cl, the organic layer was dried with MgSO4 and the solvent was evaporated under reduced pressure. The products 2 and 4 were purified by column chromatography using an end-capped silica.1 Synthesis of 3: The same procedure was followed but a Merrifield resin (300 mg, 1% cross-linking, 1.1 meq Cl/g) was used as the alkylating agent. The mixture was heated under reflux for 24 h. The polymer was filtered, washed with methanol, THF, dichloromethane and methanol and dried under vacuum at 50КC until constant weight. Synthesis of 5–8: An homogeneous mixture of the monomers and the appropriate porogen together with AIBN (1 wt % with respect to the monomers) was poured into a mold after being purged with N2. The mold was sealed, and placed in a vertical position into a water bath. The polymerization was allowed to proceed for 24 h at 80КC. The polymer was filtered, washed with THF, dichloromethane and methanol and dried under vacuum at 50КC until constant weight. 2,2'-(1,3-diphenylisopropylidene)bis[(4S)-4-tert-butyl-2-oxazoline] (2b): 1H NMR (CDCl3) d№ №(J Hz): 7.25 (m, 10H), 4.06 (dd, 2H, J = 8.4, 9.9), 3.97 (dd, 2H, J = 7.5, 8.4), 3.78 (dd, 2H, J = 7.5, 9.9), 3.44 (d, 2H, J = 14.1), 3,15 (d, 2H, J = 14.1), 0.82 (s, 18H). 13C NMR (CDCl3) d№ 166.2, 137.1, 130.5, 127.9, 126.5, 75.6, 68.3, 53.4, 39.3, 33.9, 25.8. 2,2'-[1,3-di(p-vinylphenyl)isopropylidene]bis[(4S)-4-phenyl-2-oxazoline] (4a): 1H NMR (CDCl3) d№ (J Hz): 7.3-7.1 (m, 14H), 6.84 (m, 4H), 6.61 (dd, 2H, J = 17.7, 10.6), 5.70 (d, 2H, J = 17.7), 5.15 (d, 2H, J = 10.6), 5.07 (t, 2H, J = 9.4), 4.52 (t, 2H, J = 8.7), 3.89 (t, 2H, J = 8.7), 3.41 (m, 4H). 13C NMR (CDCl3) d№ 167.4, 141.5, 136.3, 136.2, 130.6, 130.4, 128.3, 127.2, 126.6, 125.9, 113.5, 74.9, 69.5, 48.7, 38.9. 2,2'-[1,3-di(p-vinylphenyl)isopropylidene]bis[(4S)-4-tert-butyl-2-oxazoline] (4b): 1H NMR (CDCl3) d№ (J Hz): 7.33 (d, 4H, J = 8.0), 7.25 (d, 4H, J = 8.0), 6.71 (dd, 2H, J = 17.8, 10.9), 5.74 (d, 2H, J = 17.8), 5.22 (d, 2H, J = 10.9), 4.10 (dd, 2H, J = 8.8, 9.9), 3.99 (dd, 2H, J = 7.8, 8.8), 3.85 (dd, 2H, J = 7.8, 9.9), 3.48 (d, 2H, J = 14.1), 3,19 (d, 2H, J = 14.1), 0.87 (s, 18H). 13C NMR (CDCl3) d№ 165.6, 136.5, 135.6, 130.4, 125.9, 125.6, 113.0, 75.5, 68.3, 48.2, 39.1, 33.9, 25.8. [3aR-[2(3'aR*.8'aS*),3'aa№,8'aa№]]-2,2'-[1,3-di(p-vinylphenyl)isopropylidene]bis [3a,8a-dihydro-8H-indeno(1,2-d)oxazole] (4c): 1H NMR (CDCl3) d№ (J Hz): 7.7-7.5 (m, 8H), 7.12 (d, 4H, J = 10.9), 6.93 (d, 4H, J = 10.9), 6.78 (dd, 2H, J = 17.8, 10.7), 5.86 (d, 2H, J = 7.3), 5.85 (d, 2H, J = 17.8), 5.54 (t, 2H, J = 7.2), 5.41 (d, 2H, J = 10.7), 3.59 (dd, 2H, J = 18.7, 7.1), 3.52 (d, 2H, J = 15.2), 3.32 (d, 2H, J = 18.7), 3,29 (d, 2H, J = 15.2). 13C NMR (CDCl3) d№ 167.4, 141.7, 140.0, 136.8, 135.9, 135.7, 130.5, 128.6, 127.7, 126.0, 125.7, 125.4, 113.2, 83.8, 76.7, 47.9, 39.6, 38.9. Preparation of the catalysts To a solution of Cu(OTf)2 (0.2 mmol) in methanol (0.5 mL), 300 mg of polymer were added and the suspension was stirred at room temperature for 24 h. The polymer was filtered, washed with methanol and dried under vacuum at 50КC. Characterization of the catalysts Copper analyses were carried out by plasma emission spectroscopy on a Perkin-Elmer Plasma 40 emission spectrometer. Quantitative elemental analyses of the polymers were performed in duplicate on a Carlo Erba EA1108 CHNS-O instrument. Transmission FTIR spectra of self-supported wafers evacuated (<10–4 Torr) at 50 КC were obtained with a Mattson Genesis Series FTIR. IR spectra of KBr pellets of the polymers were recorded on a Perkin-Elmer 2000 FT-IR spectrophotometer. Raman spectra were obtained on the Raman accessory for the same instrument, FT-Raman Perkin-Elmer Nd:YAG Laser PSU. Cyclopropanation reactions To a suspension of the corresponding polymeric catalyst (50 mg) in a solution of styrene (358 mg, 3.44 mmol) and n-decane (150 mg) in dichloromethane (3.5 mL), was added ethyl diazoacetate (190 mg, 1.67 mmol) in the same solvent (0.5 mL), under an argon atmosphere, during 2 h using a syringe pump. The reaction was monitored by gas chromatography, and after consumption of the diazoacetate, a second portion of this reagent was added in the same way. After the reaction the catalyst was filtered off, washed with dichloromethane and air dried. The recovered catalysts were reused following the same method. The results of the reactions were determined by gas chromatography. FID from Hewlett-Packard 5890II; cross-linked methyl silicone column: 25 m ( 0.2 mm ( 0.33 m№m; helium as carrier gas, 20 p.s.i.; injector temperature: 230 АC; detector temperature: 250 АC; oven temperature program: 70 АC (3 min), 15 АC min-1 to 200 АC (5 min); retention times: ethyl diazoacetate 4.28 min, styrene 5.03 min, n-decane 6.93 min, diethyl fumarate 8.73 min, diethyl maleate 9.04 min, cis-cyclopropanes 11.84 min, trans-cyclopropanes 12.35 min. The asymmetric inductions of the reactions were also determined by gas chromatography. FID from Hewlett-Packard 5890II, Cyclodex B column: 30 m ( 0.25 mm ( 0.25 m№m; helium as carrier gas, 20 p.s.i.; injector temperature: 230 АC; detector temperature: 250 АC; oven temperature program: 125 АC isotherm; retention times: (1S,2R)-cyclopropane 28.9 min, (1R,2S)-cyclopropane 29.8 min, (1R,2R)-cyclopropane 34.3 min, (1S,2S)-cyclopropane 34.9 min. The peaks were assigned to the corresponding enantiomers by comparison with previously described results. References 1) Fraile, J. M.; Garcэa, J. I.; Gracia, D.; Mayoral, J. A.; Pires, E. J. Org. Chem. 1996, 61, 9479-9482. ]pq‚’“ЋЌНОгджзи>?рсј&';‘’459:TUЮЯјљ>?DEˆ‰Š˜в о п т  ‘ — П Р Ф Ш т у љэпэпэпэпэпэпэзпЯпЯзШУЛДЛДЛДЌДЛДЄДЄДЛДЛДœДЛДЛДЛДЄДЛ’Л’Лœ56CJOJQJCJH*OJQJCJH*OJQJ6CJOJQJ CJOJQJ5CJOJQJOJQJ CJOJQJ6CJmH sH 5CJmH sH 5CJH*OJQJmH sH 5CJOJQJmH sH CJ OJQJ9]жзрсј&'Š⠘ RЈЊфжзљFGbТіююющічхююююююююююююййеюЄ $„7dh`„7a$$a$$dha$$„`„a$њ&ўу ю я  ^ b x z ~ € *,prЎАЦШЬЮdh~€„†RlnВДМФјњPTjlpr$&46@BNPXZz|моіј0268’–ЌЎВДЊф  љёљъљтљёљъљкакактљёљъљтљёљъљкакакактљёљъљтљёљъљкакакакШкШкакакактљёљъљтљёљъљкљё5CJOJQJ56CJOJQJ5CJOJQJCJH*OJQJ CJOJQJCJH*OJQJ CJOJQJO зљ$&FbгдЄ І Ж И Ф Ц ь!№!L"M"”"—"Б"Ж"`#a#j#k#$$@%B%F%H%~%€%„%†%М%О%Т%Ф%њ%ќ%&&ƒ&…&&з&ф&х&щ&ы&э&њ&љёљщљфйЭйПйПйДйЇйЭйЭйЭйПйПйДйЭйЭйЭйЭйЭйЭйЭйЭйљёљŸљёљŸљ6CJOJQJCJEHOJQJmH sH CJOJQJmH sH  jЭ№CJOJQJmH sH 6CJOJQJmH sH CJOJQJmH sH OJQJCJH*OJQJ5CJOJQJ CJOJQJ6Т„&…&&њ&їђък$„„фўdh^„`„фўa$$dha$dh$dha$ &P Аƒ. АШA!АЅ"АЅ#Š$Š%А i0@ёџ0 Normal_HmH sH tH J`J Tэtulo 6$$dhЄ№@&a$5CJOJQJN`N Tэtulo 7$$„7dh@&`„7a$5CJOJQJFA@ђџЁF Fuente de pсrrafo predeter.\Bџџџџ]жзрсј&'Šв˜љš € ХЦуЧШъ78SГцчђ^h€€˜€€˜0€€˜0€€˜0€€h0€€X€€˜€€˜€€˜€€š0€€˜€€˜€€˜€€˜€€˜€€˜0€€˜€€˜€€˜€€˜€€˜€€X€€˜€€˜€€˜€€˜€€˜€€у њ&Тњ& њ&goˆ‰РУ$%&:=НФйоOS‚…†–šМО;Fbj№ѓєі &ЙМ-/JL   " # & ‡ ‰ Љ Д Е У Ф Ч : < ‰ ‹ І Ј У Х А Л М Ъ Ы Ю ю ѕ ] _ к м ЦбїњЕЙhk$*КОЦЬю№"=?Эйqv ?EX`sz…–ЈЕ9A€…'3FReqЉДѕћ /4^\op‘’сїј%'‰Šбв—˜јљ™ š  € ФЦтуЦШщъ68RSВДхчёђ[^Цтч[^џџJosщ Ignacio GarcэaC:\GRUPO\SupInfOL.docJosщ Ignacio Garcэa*C:\GRUPO\Articulos\OrgLet-box\SupInfOL.docJosщ Ignacio Garcэa*C:\GRUPO\Articulos\OrgLet-box\SupInfOL.docJose Ignacio Garcia3C:\GRUPO\Articulos\OrgLet-box\Revisiѓn\SupInfOL.doc^џ@€ЦЦ№ГvЦЦ ёёё ё ё ё ё ёёёbb\P@P PPPPPPP4@P PD@P$PL@џџUnknownџџџџџџџџџџџџG‡:џTimes New Roman5€Symbol3& ‡:џArial3Times?€Wingdings 271Courier"q‰№ФЉ/:I†QгJ† ЇЋщ ,!№ЅРДД€20­№пџџ\Polymer-supported bis(oxazoline)-copper complexes as catalysts in cyclopropanation reactionsJosщ Ignacio GarcэaJose Ignacio Garciaўџ р…ŸђљOhЋ‘+'Гй0Шˆј ,@ \h „  œЈАИРф]Polymer-supported bis(oxazoline)-copper complexes as catalysts in cyclopropanation reactionssolyJosщ Ignacio Garcэaosщ Normal.dotoJose Ignacio Garcia13eMicrosoft Word 9.0@ЊbT@ 'l—Р@žXB>?РЋщўџ еЭеœ.“—+,љЎ0D hp|„Œ” œЄЌД М %ф e, ­ќ ]Polymer-supported bis(oxazoline)-copper complexes as catalysts in cyclopropanation reactions Tэtulo  !ўџџџ#$%&'()*ўџџџ,-./012ўџџџ456789:ўџџџ§џџџ=ўџџџўџџџўџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџRoot Entryџџџџџџџџ РFёAG>?Р?€1Tableџџџџџџџџџџџџ"WordDocumentџџџџџџџџ"BSummaryInformation(џџџџ+DocumentSummaryInformation8џџџџџџџџџџџџ3CompObjџџџџkObjectPoolџџџџџџџџџџџџёAG>?РёAG>?Рџџџџџџџџџџџџўџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџўџ џџџџ РFDocumento Microsoft Word MSWordDocWord.Document.8є9Вq