GaCl₃-Mediated Isomerization of Donor–Acceptor Cyclopropanes into (2-Arylalkylidene)malonates

Abstract

A new process for isomerization of donor–acceptor cyclopropanes (2-arylcyclopropanedicarboxylates) by treatment with anhydrous gallium trichloride to give (2-arylalkylidene)malonates in high yields and with good selectivity has been developed. The reaction involves initial formation of a 1,2-dipolar gallium complex.

Key words

donor–acceptor cyclopropanes - cyclopropanedicarboxylates - gallium trichloride - isomerization - 1,2-dipole - alkylidenemalonates

• References and Notes


For reviews of DAC, see:
• 1a Reissig HU, Zimmer R. Chem. Rev. 2003; 103: 1151
• 1b Yu M, Pagenkopf BL. Tetrahedron 2005; 61: 321
• 1c De Simone F, Waser J. Synthesis 2009; 3353
• 1d Carson CA, Kerr MA. Chem. Soc. Rev. 2009; 38: 3051
• 1e Campbell MJ, Johnson JS, Parsons AT, Pohlhaus PD, Sanders SD. J. Org. Chem. 2010; 75: 6317
• 1f Melnikov MY, Budynina EM, Ivanova OA, Trushkov IV. Mendeleev Commun. 2011; 21: 293
• 1g Schneider TF, Kaschel J, Werz DB. Angew. Chem. Int. Ed. 2014; 53: 5504
• 1h De Nanteuil F, De Simone F, Frei R, Benfatti F, Serrano E, Waser J. Chem. Commun. 2014; 50: 10912
• 1i Novikov RA, Tomilov YV. Mendeleev Commun. 2015; 25: 1

For some recent examples of DAC reactions, see
• 2a Ivanova OA, Budynina EM, Khrustalev VN, Skvortsov DA, Trushkov IV, Melnikov MY. Chem. Eur. J. 2016; 22: 1223
• 2b Novikov RA, Potapov KV, Chistikov DN, Tarasova AV, Grigoriev MS, Timofeev VP, Tomilov YV. Organometallics 2015; 34: 4238
• 2c Wang Z, Chen S, Ren J, Wang Z. Org. Lett. 2015; 17: 4184
• 2d Ma W, Fang J, Ren J, Wang Z. Org. Lett. 2015; 17: 4180
• 2e Liu H, Yuan C, Wu Y, Xiao Y, Guo H. Org. Lett. 2015; 17: 4220
• 2f Liu Q.-J, Yan W.-G, Wang L, Zhang XP, Tang Y. Org. Lett. 2015; 17: 4014
• 2g Cheng Q.-Q, Qian Y, Zavalij PY, Doyle MP. Org. Lett. 2015; 17: 3568
• 2h Ghosh A, Pandey AK, Banerjee P. J. Org. Chem. 2015; 80: 7235
• 2i Xu H, Hu J.-L, Wang L, Liao S, Tang Y. J. Am. Chem. Soc. 2015; 137: 8006
• 2j Rakhmankulov ER, Ivanov KL, Budynina EM, Ivanova OA, Chagarovskiy AO, Skvortsov DA, Latyshev GV, Trushkov IV, Melnikov MY. Org. Lett. 2015; 17: 770
• 2k Tabolin AA, Novikov RA, Khomutova YA, Zharov AA, Stashina GA, Nelyubina YV, Tomilov YV, Ioffe SL. Tetrahedron Lett. 2015; 56: 2102
• 2l Ivanov KL, Villemson EV, Budynina EM, Ivanova OA, Trushkov IV, Melnikov MY. Chem. Eur. J. 2015; 21: 4975
• 2m Garve LK. B, Pawliczek M, Wallbaum J, Jones PG, Werz DB. Chem. Eur. J. 2016; 22: 521

For 1,2-dipolar DAC reactivity, see:
• 3a Novikov RA, Tarasova AV, Korolev VA, Timofeev VP, Tomilov YV. Angew. Chem. Int. Ed. 2014; 53: 3187
• 3b Novikov RA, Tarasova AV, Korolev VA, Shulishov EV, Timofeev VP, Tomilov YV. J. Org. Chem. 2015; 80: 8225
• 3c Novikov RA, Tarasova AV, Tomilov YV. Mendeleev Commun. 2015; 25: 341
• 3d Novikov RA, Tarasova AV, Suponitsky KY, Tomilov YV. Mendeleev Commun. 2014; 24: 346
• 3e Novikov RA, Tarasova AV, Tomilov YV. Russ. Chem. Bull. 2014; 63: 2737
• 4a Chagarovskiy AO, Ivanova OA, Rakhmankulov ER, Budynina EM, Trushkov IV, Melnikov MY. Adv. Synth. Catal. 2010; 352: 3179
• 4b Novikov RA, Korolev VA, Timofeev VP, Tomilov YV. Tetrahedron Lett. 2011; 52: 4996
• 5a Yamada K, Konishi T, Nakano M, Fujii S, Cadou R, Yamamoto Y, Tomioka K. J. Org. Chem. 2012; 77: 5775
• 5b Tomioka K, Ishiguro T, Iitaka Y, Koga K. Tetrahedron 1984; 40: 1303
• 5c Yoshiki Y, Ishiguro T. Yakugaku Zasshi 1933; 53: 73
• 5d Martelli J, Gree R. J. Chem. Soc., Chem. Commun. 1980; 355
• 5e De Nanteuil F, Waser J. Angew. Chem. Int. Ed. 2013; 52: 9009
• 5f Chevenier E, Lucatelli C, Pandya U, Wang W, Gimbert Y, Greene AE. Synlett 2004; 2693
• 5g Edwards RL, Fawcett V, Maitland DJ, Nettleton R, Shields L, Whalley AJ. S. J. Chem. Soc., Chem. Commun. 1991; 1009
• 5h Wang Z, Wang Z, Ren J. Org. Lett. 2013; 15: 5682
• 5i Zhu W, Ren J, Wang Z. Eur. J. Org. Chem. 2014; 3561
• 5j Xing S, Pan W, Liu C, Ren J, Wang Z. Angew. Chem. Int. Ed. 2010; 49: 3215
• 6 Novikov RA, Balakirev DO, Timofeev VP, Tomilov YV. Organometallics 2012; 31: 8627
• 7a Corey EJ, Chaykovsky M. J. Am. Chem. Soc. 1965; 87: 1353
• 7b Pohlhaus PD, Sanders SD, Parsons AT, Li W, Johnson JS. J. Am. Chem. Soc. 2008; 130: 8642
• 8 General Procedure for the Synthesis of (2-Arylalkylidene)malonates 3a–l All operations were performed in dry argon atmosphere. To a solution of cyclopropane 1a–l (0.6 mmol) in dry CH₂Cl₂ (5 mL) was added the solid GaCl₃ (0.66 mmol, 1.1 equiv) in one portion at 0 °C under vigorous stirring. The reaction mixture was stirred at the same temperature during 10–15 min, then MeOH (1.5 mL) was added. After that aqueous solution of HCl (5%) was added at r.t. until pH 2–3 was achieved, and the reaction mixture was extracted with CH₂Cl₂ (3 × 10 mL). The organic layer was dried over MgSO₄, and the solvent was removed in vacuo. The residue was separated by column chromatography on silica gel (eluent: from benzene to benzene–EtOAc, 10:1) to afford target (2-arylalkylidene)malonates 3a–l as thick colorless oils. If necessary, the obtained products 3a–l can be additionally purified by second column chromatography on silica gel eluting with hexane to hexane–acetone (10:1). For details, see Table 1 and Supporting Information. Analytical data for representative samples 3c,j,l are provided below. Dimethyl 2-[2-(4-Fluorophenyl)ethylidene]malonate (3c) The title compound was prepared according to the general procedure in 115 mg (76%) yield as a colorless thick oil. IR (CHCl₃): ν = 3015, 3008, 2955, 2903, 2848, 1732 (C=O), 1648, 1605, 1511, 1438, 1366, 1264 cm^–1. ¹H NMR (400.1 MHz, CDCl₃): δ = 3.59 (d, 2 H, CH₂, ³ J = 7.9 Hz), 3.77 and 3.86 (2 s, 2 × 3 H, 2 CO₂Me), 6.95–7.02 (m, 2 H, 2 m-H, ³ J _HF = 8.7 Hz), 7.07 (t, 1 H, =CH, ³ J = 7.9 Hz), 7.13–7.20 (m, 2 H, 2 o-H, ⁴ J _HF = 5.3 Hz). ¹³C NMR (100.6 MHz, CDCl₃): δ = 35.1 (CH₂), 52.41 and 52.44 (2 OMe), 115.7 (d, 2 m-CH, ² J _CF = 21.5 Hz), 128.3 (=C), 130.3 (d, 2 o-CH, ³ J _CF = 8.1 Hz), 132.8 (d, ipso-C, ⁴ J _CF = 3.2 Hz), 147.4 (=CH), 162.0 (d, p-CF, ¹ J _CF = 245.3 Hz), 164.2 and 165.6 (2 COO). ¹⁹F NMR (282.4 MHz, CDCl₃): δ = –116.6 (tt, 1F, ³ J _HF = 8.7 Hz, ⁴ J _HF = 5.3 Hz). MS: m/z (%) = 252 (2) [M⁺], 220 (16) [M⁺ – HOCH₃], 188 (21), 133 (100), 109 (36), 83 (24), 59 (93), 29 (24). HRMS: m/z calcd for C₁₃H₁₃O₄F: 253.0871 [M + H]⁺, 275.0690 [M + Na]⁺; found: 253.0867; 275.0685. Dimethyl 2-[2-(1-Naphthyl)ethylidene]malonate (3j) The title compound was prepared according to the general procedure in 283 mg (98%) yield as a colorless thick oil. IR (CHCl₃): ν = 3027, 3011, 2955, 2904, 2848, 1731 (C=O), 1645, 1598, 1511, 1488, 1438, 1396, 1372, 1303, 1268 cm^–1. ¹H NMR (400.1 MHz, CDCl₃): δ = 3.76 and 3.92 (2 s, 2 × 3 H, 2 CO₂Me), 4.12 (d, 2 H, CH₂, ³ J = 7.5 Hz), 7.23 (t, 1 H, =CH, ³ J = 7.5 Hz), 7.36 (br d, 1 H, H2′ or H4′, ³ J = 7.1 Hz), 7.42 (dd, 1 H, H3′, ³ J = 7.1 and 8.1 Hz), 7.48–7.53 (m, 1 H, H6′ or H7′), 7.53–7.58 (m, 1 H, H6′ or H7′), 7.78 (br d, 1 H, H2′ or H4′, ³ J = 8.1 Hz), 7.86–7.90 (m, 1 H, H5′ or H8′), 7.96–8.01 (m, 1 H, H5′ or H8′). ¹³C NMR (100.6 MHz, CDCl₃): δ = 33.2 (CH₂), 52.42 and 52.45 (2 OMe), 123.5, 125.7, 125.9, 126.5, 126.9, 127.9 and 128.9 [7 CH(Ar)], 128.2 (=C), 131.8, 133.6 and 134.0 [3 C(Ar)], 148.4 (=CH), 164.3 and 165.8 (2 COO). MS: m/z (%) = 284 (11) [M⁺], 252 (28) [M⁺ – HOCH₃], 220 (57), 209 (25), 192 (18), 165 (100), 152 (29), 141 (15), 115 (29), 84 (76), 75 (12), 59 (27), 47 (41), 35 (36). HRMS: m/z calcd for C₁₇H₁₆O₄: 307.0941 [M + Na]⁺; found: 307.0942. Dimethyl 2-[3,4-Dihydronaphthalen-2(1H)-ylidene]malonate (3l) The title compound was prepared according to the general procedure in 116 mg (75%) yield as a colorless thick oil. IR (CHCl₃): ν = 3012, 2954, 2905, 2846, 1730 (C=O), 1629, 1493, 1455, 1436, 1349, 1331, 1295, 1262, 1243 cm^–1. ¹H NMR (400.1 MHz, CDCl₃): δ = 2.72–2.85 (m, 4 H, CH₂CH₂), 3.74 and 3.77 (2 s, 2 × 3 H, 2 CO₂Me), 3.87 (br s, 2 H, CH₂), 7.03–7.15 [m, 4 H, 4 H(Ar)]. ¹³C NMR (100.6 MHz, CDCl₃): δ = 28.8 and 30.2 (CH₂CH₂), 35.2 (CH₂), 52.0 (2 OMe), 122.5 (=C), 126.4, 126.6, 127.4 and 128.1 [4 CH(Ar)], 134.1 and 137.2 [2 C(Ar)], 159.2 (=C), 165.6 and 165.9 (2 COO). MS: m/z (%) = 260 (7) [M⁺], 228 (45) [M⁺ – HOCH₃], 200 (16), 168 (36), 157 (11), 141 (86), 128 (100), 115 (65), 103 (7), 91 (9), 77 (20), 65 (17), 59 (51), 51 (10), 39 (26). HRMS: m/z calcd for C₁₅H₁₆O₄: 261.1121 [M + H]⁺, 283.0941 [M + Na]⁺, 299.0680 [M + K]⁺; Found: 261.1120; 283.0940; 299.0682.