Synlett, Table of Contents Synlett 2015; 26(13): 1880-1884DOI: 10.1055/s-0034-1380426 letter © Georg Thieme Verlag Stuttgart · New YorkCopper-Catalyzed Regiospecific and 1,2-Regioselective Cyclopropanation of (1Z)-1-Amino- and (1Z)-1-Oxy-1,3-butadienyl Derivatives Authors Author Affiliations Eiji Tayama* Department of Chemistry, Faculty of Science, Niigata University, Niigata 950-2181, Japan Email: tayama@chem.sc.niigata-u.ac.jp Shun Saito Department of Chemistry, Faculty of Science, Niigata University, Niigata 950-2181, Japan Email: tayama@chem.sc.niigata-u.ac.jp Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract The copper-catalyzed regiospecific and 1,2-regioselective cyclopropanation of (1Z)-1-amino- and (1Z)-1-oxy-1,3-butadienyl derivatives, which could be prepared by Z-stereoselective 1,4-elimination with α-aryl diazoesters was successfully demonstrated. This successful regiospecific protocol enabled the preparation of the corresponding 1-amino- and 1-oxy-2-vinylcyclopropane derivatives as almost single stereoisomers. Key words Key wordscycloaddition - diastereoselectivity - diazo compounds - regioselectivity - stereoselective synthesis Full Text References References and Notes Reviews: 1a Lebel H, Marcoux J.-F, Molinaro C, Charette AB. Chem. Rev. 2003; 103: 977 1b Kirmse W. Angew. Chem. Int. Ed. 2003; 42: 1088 1c Davies HM. L, Antoulinakis EG In Organic Reactions . John Wiley and Sons; New York: 2001. Chap. 1 1d Doyle MP, Mckervey MA, Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds: From Cyclopropanes to Ylides. John Wiley and Sons; New York: 1998 2a Maxwell JL, O’Malley S, Brown KC, Kodadek T. Organometallics 1992; 11: 645 2b Doyle MP, Griffin JH, Bagheri V, Dorow RL. Organometallics 1984; 3: 53 Representative examples of cyclopropanation of dienyl derivatives: 3a Guzmán PE, Lian Y, Davies HM. L. Angew. Chem. Int. Ed. 2014; 53: 13083 3b Werle T, Maas G. Adv. Synth. Catal. 2001; 343: 37 ; see also ref. 1c Representative examples of cyclopropanation of 1-substituted 1,3-butadienyl derivatives: 4a Davies HM. L, Lee GH. Org. Lett. 2004; 6: 2117 4b Hahn ND, Nieger M, Dötz KH. Eur. J. Org. Chem. 2004; 1049 ; see also ref. 1c Z-Regioselective cyclopropanation of E,Z-dienyl derivatives: 5a Davies HM. L, Doan BD. J. Org. Chem. 1998; 63: 657 5b Anciaux AJ, Demonceau A, Noels AF, Warin R, Hubert AJ, Teyssié P. Tetrahedron 1983; 39: 2169 6 Gareev VF, Sultanova RM. Biglova R. Z, Dokichev VA, Tomilov YV. Russ. Chem. Bull., Int. Ed. 2008; 57: 1784 7a Our previous studies on the 1,4-elimination: Tayama E, Toma Y. Tetrahedron 2015; 71: 554 7b Tayama E, Horikawa K, Iwamoto H, Hasegawa E. Tetrahedron 2013; 69: 2745 7c Tayama E, Otoyama S, Isaka W. Chem. Commun. 2008; 4216 7d Tayama E, Hashimoto R. Tetrahedron Lett. 2007; 48: 7950 7e Tayama E, Sugai S. Tetrahedron Lett. 2007; 48: 6163 7f Tayama E, Sugai S, Hara M. Tetrahedron Lett. 2006; 47: 7533 7g Tayama E, Sugai S. Synlett 2006; 849 8 Tayama E, Horikawa K, Iwamoto H, Hasegawa E. Tetrahedron Lett. 2014; 55: 3041 Preparation of 1-amino-2-vinyl (alkenyl) cyclopropanes: 9a de Meijere A, Chaplinski V, Winsel H, Kordes M, Stecker B, Gazizova V, Savchenko AI, Boese R, Schill F. Chem. Eur. J. 2010; 16: 13862 9b Wiedemann S, Rauch K, Savchenko A, Marek I, de Meijere A. Eur. J. Org. Chem. 2004; 631 9c Williams CM, Chaplinski V, Schreiner PR, de Meijere A. Tetrahedron Lett. 1998; 39: 7695 Representative examples of preparation of 1-amino-2-vinylcyclopropane-1-carboxylic acid derivatives: 10a Lou S, Cuniere N, Su B.-N, Hobson LA. Org. Biomol. Chem. 2013; 11: 6796 10b Tang W, Wei X, Yee NK, Patel N, Lee H, Savoie J, Senanayake CH. Org. Process Res. Dev. 2011; 15: 1207 10c Crane ZD, Nichols PJ, Sammakia T, Stengel PJ. J. Org. Chem. 2011; 76: 277 Preparation of 1-oxy-2-vinyl (alkenyl) cyclopropanes: 11a McGaffin G, Grimm B, Heinecke U, Michaelsen H, de Meijere A, Walsh R. Eur. J. Org. Chem. 2001; 3559 11b Militzer H.-C, Schömenauer S, Otte C, Puls C, Hain J, Bräse S, de Meijere A. Synthesis 1993; 998 11c Davies HM. L, Hu B. J. Org. Chem. 1992; 57: 4309 11d de Meijere A, Schulz T.-J, Kostikov RR, Graupner F, Murr T, Bielfeldt T. Synthesis 1991; 547 12 A representative review: Hudlicky T, Reed JW. Angew. Chem. Int. Ed. 2010; 49: 4864 13 A study on cyclopropanation of (E)- and (Z)-enamides: Lu T, Song Z, Hsung RP. Org. Lett. 2008; 10: 541 14 When the reaction was carried out at 0 °C, (Z)-3aa and 4aa were obtained in 7% combined yield [(E)-3aa/(Z)-3aa/4aa = 0:51:49] with the recovery of the substrates [(Z)-1a, 84%; 2a, 86%]. 15 Representative Procedure A solution of (Z)-1e (65 mg, 0.33 mmol) and 2a (77 mg, 0.30 mmol) in CH2Cl2 (3.0 mL) was added to (MeCN)4CuPF6 (2 mg, 0.005 mmol) in a flask at r.t. and stirred for 2 h under an argon atmosphere. Extractive workup and purification of the residue by chromatography on silica gel (CH2Cl2–MeOH = 200:1 to 40:1 as the eluent) afforded a mixture of (E)-3ea and 4ea [103 mg, (E)-3ea/4ea = 5:95; (E)-3ea, 4% yield; 4ea, 77% yield] as a white solid. Analytical Data of 4ea IR (KBr): 2982, 2935, 2873, 1728, 1711, 1693, 1490, 1479, 1447, 1369, 1317, 1294, 1250, 1209, 1188, 1156, 1128, 1077, 1066, 1011, 974, 920, 900, 827, 772, 762, 732 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.43 (2 H, ddd, J = 8.4, 2.2, 2.2 Hz, ArH), 7.15 (2 H, ddd, J = 8.4, 2.2, 2.2 Hz, ArH), 5.50–5.40 (1 H, m, CH=CH2), 5.31–5.18 (2 H, m, CH=CH 2), 4.95 (1 H, d, J = 7.2 Hz, 2-H), 3.90 [1 H, br, CH(CH3)2], 3.61 (3 H, s, OCH3), 3.59–3.47 [1 H, m, CH(CH3)2], 2.89–2.77 (1 H, m, 3-H), 1.40–1.10 [6 H, m, CH(CH 3)2], 0.89 [3 H, d, J = 6.4 Hz, CH(CH 3)2], 0.82 [3 H, d, J = 6.4 Hz, CH(CH 3)2]. 13C NMR (100 MHz, CDCl3): δ = 171.9, 154.1, 134.2, 131.11, 131.08, 130.7, 121.7, 119.0, 60.6, 60.5, 52.7, 46.4, 46.0, 36.6, 33.9, 20.7, 20.6, 20.5, 20.3. ESI-HRMS: m/z [M + H]+ calcd for C20H27BrNO4: 424.1118; found: 424.1111. 16 A study on decomposition of α-aryl diazoesters with rhodium(II) catalysts: Qu Z, Shi W, Wang J. J. Org. Chem. 2001; 66: 8139 Supplementary Material Supplementary Material Supporting Information (PDF)
