Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany

2 The Donor-Acceptor Cyclopropanes as Three-Carbon Component in [4+3]-Cycloaddition. Reaction with 1,3-Diphenylisobenzofuran lga A. Ivanova,* Ekaterina M. Budynina, Yuri K. Grishin, Igor V. Trushkov and Pavel V. Verteletskii [*] Dr..A. Ivanova Department of Chemistry Lomonosov Moscow State University Leninskie gory 1-3; Moscow (Russia) Fax: (+7) Supporting information: Page 1

3 Experimental General Melting points (mp): Electrothermal 9100 capillary melting point apparatus, values uncorrected. NMR spectra (400 MHz) were recorded on a Bruker Avance-400 spectrometer at room temperature; the chemical shifts δ were measured in ppm with respect to the solvent (CDCl 3, 1 Н: δ = 7.26 ppm, 13 C: δ = 77.1 ppm). Coupling constants (J) are in Hz. Splitting patterns of an apparent multiplet associated with an averaged coupling constant were designed as s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), dd (doublet of doublets ), dq (doublet of quartets) and br (broadened). Column chromatography was performed on silica gel 60 ( mesh, Merck). 1,1-Diphenylisobenzofuran, Yb(Tf) 3 are available commercially. 2-Aryl-1,1- cyclopropane diesters 1 were prepared by published procedures. 1 All the reactions were carried out using freshly distilled and dry solvents from solvent stills. CEt CEt F Diethyl 2-(4-fluorophenyl)cyclopropane-1,1-dicarboxylate (1b). Bp C / 2 mm Yield 80 %. 1 Н NMR (CDCl 3 ): δ = 0.87 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 1.25 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 1.65 (dd, 2 J = 5.2, 3 J = 9.1 Hz, 1 Н, CH 2 ), 2.09 (dd, 2 J = 5.2, 3 J = 7.8 Hz, 1 Н, CH 2 ), 3.15 (dd, 3 J = 9.1, 3 J = 7.8 Hz, 1 Н, CH), (m, 2H, CH 2 ), (m, 2H, CH 2 ), (m, 2 H,CH), (m, 2 H, CH). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), ( 1 J CH = 165 Hz, CH 2, cy-pr), ( 1 J CH = 166 Hz, CH, cy-pr), (C), (CH 2 ), (CH 2 ), (d, 2 J CF = 21 Hz, CH, ), (d, 3 J CF = 8 Hz, CH, ), (C, ), (d, 1 J CF = 246 Hz, CF), (), (). Anal. Calcd for C 15 H 17 F 4 : C, 64.28; H, Found: C, 64.02; H, Supporting information: Page 2

4 General Procedure for Yb(Tf) 3 -Catalyzed Reactions of 1,1-diphenylisobenzofuran with Cyclopropane Diesters 1,1-Diphenylisobenzofuran (284 mg, 1.05 mmol), 2-aryl-1,1-carboethoxycyclopropane (1 mmol) and Yb(Tf) 3 (31 mg, 0.05 mmol) were dissolved in dry CH 2 Cl 2 (4 ml) and stirred with activated 4 Å molecular sieves under argon at room temperature or at refluxing for the time indicated in the Table 2. The progress of the reaction was monitored by TLC, 1 Н NMR. Since the cyclopropane diester disappearance, the reaction mixture was filtered, the solvent was evaporated under vacuum, and the residue was purified by column chromatography (Si 2, eluent: hexane CHCl 3, 1:1). 3a Diethyl 5,8,9-triphenyl-5,7,8,9-tetrahydro-6H-5,9-epoxybenzo[7]annulene-6,6- dicarboxylate (3a) Mp C (B). Yield 85%; R f 0.59 (B), R f 0.49 (A) (CHCl 3 ). A (exo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.68 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 1.25 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 2.53 (dd, 2 J = 14.3, 3 J = 6.8 Hz, 1 Н, CH 2 ), 2.76 (dd, 2 J = 14.3, 3 J = 1.5 Hz, 1 Н, CH 2 ), 3.10 (dq, 2 J = 10.8, 3 J = 7.2 Hz, 1 H, CH 2 ), 3.69 (dq, 2 J = 10.8, 3 J = 7.2 Hz, 1 H, CH 2 ), 3.72 (dd, 3 J = 6.8, 3 J = 1.5 Hz, 1 Н, CH), 4.21 (dq, 2 J = 10.8, 3 J = 7.2 Hz, 1 H, CH 2 ), (m, 1 H, CH 2 ), (m, 1 H, ), (m, 1 H, ), (m, 2 H, ), (m, 9 H, ), (m, 2 H, ), (m, 2 H, ), (m, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (C), (CH 2 ), (CH 2 ), (C), (C), (CH), (CH), (2 CH), (CH), (2 CH), (2 CH), (CH), (2 CH), (2 CH), (3 CH), (2 CH), (C), (C), (C), (C), (C), (), (). Supporting information: Page 3

5 B (endo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.91 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 1.27 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 2.02 (dd, 2 J = 14.1, 3 J = 12.2 Hz, 1 Н, CH 2 ), 2.69 (dd, 2 J = 14.1, 3 J = 4.6 Hz, 1 Н, CH 2 ), 3.93 (dd, 3 J = 12.2, 3 J = 4.6 Hz, 1 Н, CH), (m, 2 H, CH 2 ), (m, 2 H, CH 2 ), 6.92 (d, 3 J = 7.7 Hz, 2 H, ), 7.15 (d, 3 J = 7.6 Hz, 1 H, ), (m, 13 H, ), 7.67 (d, 3 J = 7.6 Hz, 1 H, ), 7.84 (d, 3 J = 7.8 Hz, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (CH 2 ), (C), (CH 2 ), (C), (C), (CH), (CH), (2 CH), (2 CH), (CH), (CH), (2 CH), (CH), (2 CH), (2 CH), (2 CH), (2 CH), (C), (C), (C), (C), (C), (), (). Anal. Calcd for С 35 Н 32 5 : C, 78.92; H, Found: С, 78.65; Н, p-f-c 6 H 4 3b Diethyl 5,9-diphenyl-8-(4-fluorophenyl)-5,7,8,9-tetrahydro-6H-5,9-epoxybenzo[7]annulene- 6,6-dicarboxylate (3b) Colorless solid; mp C (A). Yield 90%; R f 0.52 (B), R f 0.23 (A) (CHCl 3 ). A (exo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.74 (t, 3 J = 7.1 Hz, 3 H, CH 3 ), 1.25 (t, 3 J = 7.1 Hz, 3 H, CH 3 ), 2.52 (dd, 2 J = 14.3, 3 J = 6.7 Hz, 1 H, CH 2 ), 2.71 (dd, 2 J = 14.3, 3 J = 1.2 Hz, 1 H, CH 2 ), 3.18 (dq, 2 J = 10.9, 3 J = 7.1 Hz, 1 H, CH 2 ), 3.71 (dd, 3 J = 6.7, 3 J = 1.2 Hz, 1 H, CH), 3.74 (dq, 2 J = 10.9, 3 J = 7.1 Hz, 1 H, CH 2 ), (m, 1 H, CH 2 ), (m, 1 H, CH 2 ), (m, 2 H, CH, ), (m, 1 H, CH, ), (m, 3 H, CH, ), (m, 6 H, ), (m, 2 H, ), 7.59 (d, 3 J = 7.8 Hz, 2 H, ), 7.83 (d, 3 J = 7.8 Hz, 2 H, ). Supporting information: Page 4

6 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (C), (CH 2 ), (CH 2 ), (C), (C), (d, 2 J CF = 21 Hz, 2 CH, ), (CH, ), (CH, ), (2 CH, ), (2 CH, ), (CH, ), (CH, ), (CH, ), (2 CH, ), (3 CH, ), (d, 3 J CF = 8 Hz, 2 CH, ), (C, ), (C, ), (C, ), (C, ), (C, ), (d, 1 J CF = 244 Hz, C, ), (), (). Exo-configuration was confirmed by X-Ray diffraction (Figure 1). Figure 1. Perspective view of the molecule 3b (exo-isomer) showing the atom labelling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at 30 % level. Hydrogen atoms are omitted for clarity. B (endo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.91 (t, 3 J = 7.2 Hz, 3 H, CH 3 ), 1.28 (t, 3 J = 7.2 Hz, 3 H, CH 3 ), 1.96 (dd, 2 J = 13.6, 3 J = 12.3 Hz, 1 H, CH 2 ), 2.66 (dd, 2 J = 13.6, 3 J = 4.7 Hz, 1 H, CH 2 ), 3.93 (dd, 3 J = 12.3, 3 J = 4.7 Hz, 1 H, CH), (m, 2 H, CH 2 ), (m, 2 H, CH 2 ), (m, 2 H, ), (m, 2 H, ), (m, 1 H, ), (m, 10 H, ), (m, 1 H, ), (m, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (CH 2 ), (C), (CH 2 ), (C), (C), (d, 2 J CF = 21 Hz, 2 CH, ), (CH, ), (2 CH, ), (CH, ), (2 CH, ), (CH, ), (CH, ), (CH, ), (CH, ), (2 CH, ), (2 CH, ), (d, 3 J CF = 8 Hz, 2 CH, ), (C), (C), (C), (C), (C), (d, 1 J CF = 244 Hz, C, ), (), (). Anal. Calcd for С 35 Н 31 F 5 : C, 76.35; H, Found: С, 76.01; Н, Supporting information: Page 5

7 p-me-c 6 H 4 3c Diethyl 5,9-diphenyl-8-(4-methoxyphenyl)-5,7,8,9-tetrahydro-6H-5,9-epoxybenzo- [7]annulene-6,6-dicarboxylate (3c) Mp C (A). Yield 86%; R f 0.61 (B), R f 0.35 (A) (CHCl 3 ). A (exo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.75 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 1.26 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 2.53 (dd, 2 J = 14.2, 3 J = 6.6 Hz, 1 Н, CH 2 ), 2.75 (dd, 2 J = 14.2, 3 J = 1.2 Hz, 1 Н, CH 2 ), (m, 1 H, CH 2 ), 3.71 (c, 3 H, CH 3 ), 3.73 (m, 1 Н, CH), (m, 1 H, CH 2 ), (m, 2 H, CH 2 ), 6.71 (d, 3 J = 8.3 Hz, 2 H, ), 6.91 (d, 3 J = 7.4 Hz, 1 H, ), (m, 9 H, ), (m, 2 H, ), 7.64 (d, 3 J = 7.6 Hz, 2 H, ), 7.88 (m, 3 J = 7.8 Hz, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (CH 3 ), (C), (CH 2 ), (CH 2 ), (C), (C), (2 CH), (CH), (CH), (2 CH), (2 CH), (2 CH), (CH), (2 CH), (3 CH), (2 CH), (C), (C), (C), (C), (C), (C), (), (). B (endo-isomer; NMR shifts and J values were deduced from spectra of mixture with exoisomer) 1 Н NMR (CDCl 3 ): δ = 0.93 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 1.28 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 2.01 (dd, 2 J = 13.7, 3 J = 12.6 Hz, 1 Н, CH 2 ), 2.65 (dd, 2 J = 13.7, 3 J = 4.6 Hz, 1 Н, CH 2 ), 3.82 (c, 3 H, CH 3 ), 3.93 (dd, 3 J = 12.6, 3 J = 4.6 Hz, 1 Н, CH), (m, 2 H, CH 2 ), (m, 2 H, CH 2 ), (m, 4 H, ), (m, 1 H, ), (m, 7 H, ), (m, 2 H, ), (m, 2 H, ), (m, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (CH 3 ), (C), (CH 2 ), (CH 2 ), (C), (C), (2 CH), (CH), (2 CH), (2 CH), (2 CH), (2 CH), (CH), (2 CH), (2 CH), (2 CH), (C), (C), (C), (C), (C), (C), (), (). Anal. Calcd for С 36 Н 34 6 : C, 76.86; H, Found: С, 76.78; Н, Supporting information: Page 6

8 Me C 2 Me C 2 Me 3d Me Me Dimethyl 5,9-diphenyl-8-(3,4,5-trimethoxyphenyl)-5,7,8,9-tetrahydro-6H-5,9-epoxybenzo- [7]annulene-6,6-dicarboxylate (3d) Mp C (A). Yield 89%; R f 0.35 (B), R f 0.20 (A) (CHCl 3 ). A (exo-isomer) 1 Н NMR (CDCl 3 ): δ = 2.51 (dd, 2 J = 14.3, 3 J = 6.6 Hz, 1 Н, CH 2 ), 2.68 (br. d, 2 J = 14.3 Hz, 1 Н, CH 2 ), 3.03 (s, 1 H, CH 3 ), 3.62 (br. d, 3 J = 6.6 Hz, 1 Н, CH), 3.74 (c, 6 H, 2 CH 3 ), 3.75 (s, 3 H, CH 3 ), 3.77 (s, 3 H, CH 3 ), 6.68 (s, 2 H, ), 6.92 (d, 3 J = 6.8 Hz, 1 H, ), (m, 3 H, ), (m, 4 H, ), 7.48 (t, 3 J = 7.8 Hz, 2 H, ), 7.62 (d, 3 J = 7.8 Hz, 2 H, ), 7.77 (d, 3 J = 7.8 Hz, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 2 ), (CH), (CH 3 ), (CH 3 ), (2 CH 3 ), (C), (CH 3 ), (C), (C), (2 CH), (CH), (CH), (2 CH), (2 CH), (3 CH), (2 CH), (3 CH), (C), (C), (C), (C), (C), (C), (2 C), (), (). B (endo-isomer) 1 Н NMR (CDCl 3 ): δ = 1.96 (dd, 2 J = 13.8, 3 J = 12.6 Hz, 1 Н, CH 2 ), 2.71 (dd, 2 J = 13.8, 3 J = 4.7 Hz, 1 Н, CH 2 ), 3.57 (c, 3 H, CH 3 ), 3.67 (c, 6 H, 2 CH 3 ), 3.82 (dd, 3 J = 12.6, 3 J = 4.7 Hz, 1 Н, CH), 3.81 (s, 3 H, CH 3 ), 3.87 (s, 3 H, CH 3 ), 6.08 (s, 2 H, ), (m, 9 H, ), (m, 1 H, ), 7.68 (d, 3 J = 7.8 Hz, 1 H, ), 7.72 (d, 3 J = 7.8 Hz, 1 H, ), 7.80 (d, 3 J = 7.8 Hz, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 2 ), (CH), (CH 3 ), (CH 3 ), (2 CH 3 ), (CH 3 ), (C), (C), (C), (2 CH), (CH), (2 CH), (CH), (CH), (3 CH), (2 CH), (CH), (CH), Supporting information: Page 7

9 (C), (C), (C), (C), (C), (2 C), (), (). Anal. Calcd for С 36 Н 34 8 : C, 72.71; H, Found: С, 72.63; Н, S 3e Diethyl 8-(2-thienyl)-5,9-diphenyl-5,7,8,9-tetrahydro-6H-5,9-epoxybenzo[7]annulene-6,6- dicarboxylate (3e) Mp C (A). Yield 92%; R f 0.54 (B), R f 0.33 (A) (CHCl 3 ). A (exo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.86 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 1.28 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 2.52 (dd, 2 J = 14.2, 3 J = 6.2 Hz, 1 Н, CH 2 ), 2.85 (br. d, 2 J = 14.2 Hz, 1 Н, CH 2 ), (m, 1 H, CH 2 ), (m, 1 H, CH 2 ), 4.00 (br. d, 3 J = 6.2 Hz, 1 Н, CH), (m, 1 H, CH 2 ), (m, 2 H, CH 2 ), 6.74 (dd, 3 J = 3.5, 3 J = 5.0 Hz, 1 Н, Th), 6.94 (d, 3 J = 7.6 Hz, 1 H, ), (m, 2 H, Th), (m, 6 H, ), 7.52 (t, 3 J = 7.8 Hz, 2 H, ), 7.68 (d, 3 J = 7.8 Hz, 2 H, ), 7.87 (d, 3 J = 7.8 Hz, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), 58.81(C), (CH 2 ), (CH 2 ), (C), (C), (CH), (CH), (CH), (2 CH), (2 CH), (CH), (CH), (CH), (CH), (3 CH), (2 CH), (CH), (C), (C), (C), (C), (C), (), (). B (endo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.92 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 1.30 (t, 3 J = 7.1 Hz, 3 Н, CH 3 ), 1.92 (dd, 2 J = 13.6, 3 J = 12.1 Hz, 1 Н, CH 2 ), 2.86 (dd, 2 J = 13.6, 3 J = 4.7 Hz, 1 Н, CH 2 ), (m, 2 H, CH 2 ), (m, 2 H, CH 2 ), 4.44 (dd, 3 J = 4.7, 3 J = 12.1 Hz, 1 Н, CH), 6.64 (d, 3 J = 3.4 Hz, 1 H, Th), 6.88 (dd, 3 J = 3.4 Hz, 3 J = 5.0 Hz, 1 H, Th), (m, 10 H,, Th), (m, 2 H, ), 7.68 (d, 3 J = 7.7 Hz, 1 H, ), 7.81 (d, 3 J = 7.8 Hz, 2 H, ). Supporting information: Page 8

10 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (CH 2 ), (C), (CH 2 ), (C), (C), (CH), (CH), (CH), (2 CH), (CH), (CH), (CH), (CH), (CH), (2 CH), (2 CH), (3 CH), (C), (C), (C), (C), (C), (), (). Anal. Calcd for С 33 Н 30 5 S: C, 73.58; H, Found: С, 73.35; Н, f Diethyl 8-(2-furyl)-5,9-diphenyl-5,7,8,9-tetrahydro-6H-5,9-epoxybenzo[7]annulene-6,6- dicarboxylate (3f) Mp C (A). Yield 84%; R f 0.57 (B), R f 0.34 (A) (CHCl 3 ). A (exo-isomer) 1 Н NMR (CDCl 3 ): δ = 0.95 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 1.28 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 2.29 (dd, 2 J = 14.4, 3 J = 6.0 Hz, 1 Н, CH 2 ), 2.92 (dd, 2 J = 14.4, 3 J = 1.5 Hz, 1 Н, CH 2 ), 3.44 (dq, 2 J = 10.9, 3 J = 7.2 Hz, 1 H, CH 2 ), 3.77 (dd, 3 J = 6.0, 3 J = 1.5 Hz, 1 Н, CH), 3.85 (dq, 2 J = 10.9, 3 J = 7.2 Hz, 1 H, CH 2 ), (m, 2 H, CH 2 ), 5.95 (d, 3 J = 3.2 Hz, 1 H, Fu), 6.07 (dd, 3 J = 3.2 Hz, 3 J = 1.7 Hz, 1 H, Fu), (m, 1 H, ), (m, 10 H, Fu, ), (m, 2 H, ), (m, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), 58.84(C), (CH 2 ), (CH 2 ), (C), (C), (CH), (CH), (CH), (CH), (2 CH), (2 CH), (CH), (CH), (CH), (2 CH), (3 CH), (CH), (C), (C), (C), (C), (C), (), (). B (endo-isomer; NMR shifts and J values were deduced from spectra of mixture with endoisomer) 1 Н NMR (CDCl 3 ): δ = 0.90 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 1.29 (t, 3 J = 7.2 Hz, 3 Н, CH 3 ), 1.90 (dd, 2 J = 13.7, 3 J = 12.2 Hz, 1 Н, CH 2 ), 2.77 (dd, 2 J = 13.7, 3 J = 4.9 Hz, 1 Н, CH 2 ), (m, Supporting information: Page 9

11 2 H, CH 2 ), (m, 3 H, CH, CH 2 ), 5.89 (d, 3 J = 3.3 Hz, 1 H, Fu), 6.31 (dd, 3 J = 2.0, 3 J = 3.3 Hz, 1 H, Fu), 7.10 (m, 1 H, ), (m, 11 H, Fu, ), (m, 1 H, ), (m, 2 H, ). 13 С NMR (CDCl 3 ): δ = (CH 3 ), (CH 3 ), (CH 2 ), (CH), (CH 2 ), (C), (CH 2 ), (C), (C), (CH), (CH), (CH), (CH), (2 CH), (CH), (CH), (2 CH), (2 CH), (CH), (2 CH), (CH), (C), (CH), (C), (C), (C), (C), (), (). Anal. Calcd for С 33 Н 30 6 : C, 75.86; H, Found: С, 75.86; Н, General Procedure for Yb(Tf) 3 -Catalyzed Reactions Decomposition of Cycloadducts 3 A mixture Yb(Tf) 3 (31 mg, 0.05 mmol) and the cycloadduct (1.0 mmol) in dry benzene (4 ml) was refluxed under argon for the time indicated in the Table 3. When the reaction was complete (monitored by TLC, 1 Н NMR), the reaction mixture was concentrated under reduced pressure, and the residue was purified by column chromatography (Si 2, eluent: hexane CHCl 3, 1:1). 4a {2-[(Z)-1,2-diphenylvinyl]phenyl}(phenyl)methanone (4a) Mp C. Yield 85%; R f 0.85 (CHCl 3 ). 1 Н NMR (CDCl 3 ): δ = 6.92 (br. s, 1 H), (m, 2 H), (m, 3 H), (m, 7 H), (m, 6 H), (m, 1 H). 13 С NMR (CDCl 3 ): δ = (CH), (CH), (CH), (2 CH), (2 CH), (2 CH), (2 CH), (CH), (2 CH), (CH), (2 CH), (CH), (CH), (CH), (C), (C), (C), (C), (C), (C), (C). Supporting information: Page 10

12 Anal. Calcd for С 27 Н 20 : C, 89.97; H, Found: С, 89.82; Н, p-f- 4b (Z)-{2-[2-(4-Fluorophenyl)-1-phenylvinyl]phenyl}(phenyl)methanone (4b). Yellow-green solid. Mp C. Yield 81%; R f 0.60 (CHCl 3 ). 1 Н NMR (CDCl 3 ): δ = (m, 2 H), 6.87 (s, 1 H, CH=), (m, 2 H), (m, 7 H), (m, 6 H), (m, 1 H). 13 С NMR (CDCl 3 ): δ = (d, 2 J CF = 21 Hz, 2 CH), (CH), (2 CH), (2 CH), (2 CH), (2 CH), (CH), (2 CH), (CH), (d, 3 J CF = 8 Hz, 2 CH), (CH), (CH), (C), (C), (C), (C), (C), (C), (d, 1 J CF = 247 Hz, C), (C=). Anal. calcd for C 27 H 19 F: C, 85.69; H, Found: C, 85.38; H, Z-configuration was confirmed by X-Ray diffraction (Figure 2). Figure2. Perspective view of the molecule 4b showing the atom labelling scheme. Nonhydrogen atoms are represented by Gaussian ellipsoids at 30 % level. Hydrogen atoms are omitted for clarity. Supporting information: Page 11

13 S (enyl){2-[(z)-1-phenyl-2-(2-thienyl)vinyl]phenyl}methanone (4c) Mp C. Yield 86%; R f 0.76 (CHCl 3 ). 1 Н NMR (CDCl 3 ): δ = (m, 2 H), (m, 1 H), 7.17 (s, 1 H), (m, 7 H), (m, 1 H), (m, 6 H). 13 С NMR (CDCl 3 ): δ = (CH), (CH), (2 CH), (CH), (2 CH), (CH), (2 CH), (2 CH), (2 CH), (CH), (CH), (CH), (CH), (C), (C), (C), (C), (C), (C), (C). Anal. Calcd for С 25 Н 18 S: C, 81.93; H, Found: С, 81.69; Н, c 1. E. J. Corey, M. Chaykovsky. J. Am. Chem. Soc. 1965, 86, Supporting information: Page 12

14 CEt CEt F 1b Supporting information: Page 13

15 3a exo-isomer Supporting information: Page 14

16 3a endo-isomer Supporting information: Page 15

17 p-f-c 6 H 4 3b exo-isomer Supporting information: Page 16

18 p-f-c 6 H 4 3b endo-isomer Supporting information: Page 17

19 p-me-c 6 H 4 3c exo-isomer Supporting information: Page 18

20 p-me-c 6 H 4 3c Mixture of endo- and exo-isomers Supporting information: Page 19

21 Me Me C 2 Me C 2 Me 3d Me exo-isomer Supporting information: Page 20

22 Me Me C 2 Me C 2 Me 3d Me endo-isomer Supporting information: Page 21

23 S 3e exo-isomer Supporting information: Page 22

24 S 3e endo-isomer Supporting information: Page 23

25 3f exo-isomer Supporting information: Page 24

26 3f Mixture of endo- and exo-isomers Supporting information: Page 25

27 4a Supporting information: Page 26

28 p-f-c 4 H 6 4b Supporting information: Page 27

29 S 4c Supporting information: Page 28

30 Table S1. Ab initio calculated (HF/6-31G) dihedral angles HC 7 C 8 H in exo- and endo-isomers of 3a, J HH coupling constants calculated from ab initio data using the Karplus equation and the corresponding J HH coupling constants determined by NMR 1 H. Isomer Θ (eq-hc 7 C 8 H) J HH, Hz Θ (ax-hc 7 C 8 H) J HH, Hz Experimental J HH values, Hz exo 80.3º º ; 6.7 endo 52.6º º ; 12.3 Supporting information: Page 29

31 Results of ab initio calculations at HF/6-31G level. S1 Endo-3a HF Energy = Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z Supporting information: Page 30

32 Exo-3a HF Energy = Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z Supporting information: Page 31

33 Supporting information: Page 32

34 (Z)-4a HF Energy = Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z Supporting information: Page 33

35 (E)-4a HF Energy = Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z Supporting information: Page 34

36 References: S1) Gaussian 98; M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain,. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. chterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. rtiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1998 Supporting information: Page 35