Supporting Information. Gold-Catalyzed Oxime-Oxime Rearrangement

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1 Supporting Information Gold-Catalyzed Oxime-Oxime Rearrangement Sinem Güven, Merve Sinem Özer, Serdal Kaya,, Nurettin Menges,, Metin Balci,* Middle East Technical University, Department of Chemistry, Ankara, Turkey Giresun University, Department of Chemistry, Giresun, Turkey Yüzüncü Yil University, Faculty of Pharmacy, Van, Turkey Contents 1 Experimental Section S4 Synthesis of 5a S4 Synthesis of 5b S4 Synthesis of 6a S5 Synthesis of 6b S5 Synthesis of 6c S5 General procedure for Sonogashira couplings 7a-c and 10a,b S6 Synthesis of 7a S6 Synthesis of 7b S6 Synthesis of 7c S7 Synthesis of 9a S7 Synthesis of 9b S8 Synthesis of 10a S8 Synthesis of 10b S9 General procedure for oxime generation 11a-j S9 Synthesis of 11a S9 Synthesis of 11b S10 Synthesis of 11c S10 Synthesis of 11d S11 Synthesis of 11e S11 S1

2 Synthesis of 11f S12 Synthesis of 11g S12 Synthesis of 11h S13 Synthesis of 11i S13 Synthesis of 11j S14 General procedure gold-catalyzed cyclization of oxime S14 Synthesis of 12a S14 Synthesis of 12b S15 Synthesis of 12c S15 General procedure for oxime-oxime transformation reactions S15 Synthesis of 13a S15 Synthesis of 13b S16 Synthesis of 13c S16 Synthesis of 13d S17 Synthesis of 13e S17 Synthesis of 13f S18 Synthesis of 13g S18 Synthesis of 14 S19 Synthesis of 15 S19 Synthesis of 16 S20 Synthesis of 17 S20 Synthesis of 13c S21 Geometry optimized structures S21 Cartesian coordinates for the optimized structures S22 References S24 2. NMR Spectra of all compounds S25 Table of figures Figure 2: 1 H and 13 C NMR Spectra of 5a Figure 3: 1 H and 13 C NMR Spectra of 6a Figure 4: 1 H and 13 C NMR Spectra of 6b Figure 5: 1 H and 13 C NMR Spectra of 6c Figure 6: 1 H and 13 C NMR Spectra of 7a S25 S26 S27 S28 S29 S2

3 Figure 7: 1 H and 13 C NMR Spectra of 7b Figure 8: 1 H and 13 C NMR Spectra of 7c Figure 9: 1 H and 13 C NMR Spectra of 9a Figure 10: 1 H and 13 C NMR Spectra of 9b Figure 11: 1 H and 13 C NMR Spectra of 10a Figure 12: 1 H and 13 C NMR Spectra of 10b Figure 13: 1 H and 13 C NMR Spectra of 11a Figure 14: 1 H Spectrum of 11b and 13 C NMR Spectrum of a mixture of 6b and 11b. Figure 15: 1H and 13C NMR Spectra of 11c Figure 16: 1H and 13C NMR Spectra of 11d Figure 17: 1 H and 13 C NMR Spectra of 11e Figure 18: 1 H and 13 C NMR Spectra of 11f Figure 19: 1 H and 13 C NMR Spectra of 11g Figure 20: 1 H and 13 C NMR Spectra of 11h Figure 21: 1 H and 13 C NMR Spectra of 11i Figure 22: 1 H and 13 C NMR Spectra of 11j Figure 23: 1 H and 13 C NMR Spectra of 12a Figure 24: 1 H and 13 C NMR Spectra of 12b Figure 25: 1 H and 13 C NMR Spectra of 12c Figure 26: 1 H and 13 C NMR Spectra of 13a Figure 27: 1 H and 13 C NMR Spectra of 13b Figure 28: HMBC Spectrum of 13b Figure 29: 1 H and 13 C NMR Spectra of 13c Figure 30: 1 H and 13 C NMR Spectra of 13d Figure 31: 1 H NMR Spectrum of 13e Figure 32: 1 H and 13 C NMR Spectra of 13f Figure 33: 1 H and 13 C NMR Spectra of 13g Figure 34: 1 H and 13 C NMR Spectra of 14 Figure 35: 1 H and 13 C NMR Spectra of 15 Figure 36: 1 H and 13 C NMR Spectra of 16 Figure 37: 1 H and 13 C NMR Spectra of 17 Figure 38: 1 H and 13 C NMR Spectra of 13c S30 S31 S32 S33 S34 S35 S36 S37 S38 S39 S40 S41 S42 S44 S45 S45 S46 S47 S48 S49 S50 S51 S52 S53 S54 S55 S56 S57 S58 S59 S60 S61 S3

4 Experimental Section General Methods. All reagents were used as purchased from commercial suppliers without further purification. Proton nuclear magnetic resonance spectra ( 1 H NMR and 13 C-NMR) were recorded on an instrument 400 MHz (100 MHz). Column chromatography was performed on silica gel (60-mesh). TLC was carried out on 0.2 mm silica gel 60 F254 analytical aluminum plates. High resolution Mass spectra were recorded by LC-MS TOF electrospray ionization technique. Chemicals and all solvents were commercially available and used without further purification. Infrared (IR) spectra were recorded in the range cm-1 via ATR diamond. Melting points were measured using melting point apparatus and were uncorrected. Evaporation of solvents was performed at reduced pressure, using a rotary vacuum evaporator. 1H-pyrrole-2-carbaldehyde (5a). To a solution of POCl3 (34.25 g, mol) and DMF (19.61 g, mol) in dry ether (60 ml), pyrrole (15.0 g, mol) was added dropwise in an ice-bath. After the reaction was stirred for 24 h, the mixture was quenched with sat. NaHCO3 solution until ph was brought around 7. Then the extraction was performed with ethyl acetate. (Each 200 ml aqueous phase was washed with 250 ml ethyl acetate with 3 times.) Dried over MgSO4 and then the evaporation of solvent under the reduced pressure gave residue. Separation by column chromatography eluted with hexane:ethyl acetate (3:1) gave successively 1H-pyrrole-2-carbaldehyde (5a) as a needle shaped colorless crystals (13.5 g, 64%), mp C. 1 1 H-NMR (400 MHz, CDCl3) δ (br s, 1H, -NH), 9.51 (d, J = 1.0, 1H, -CH), 7.18 (br s, 1H, H-3), 7.01 (ddd, J54 = 3.8 Hz, J53 = 2.3 Hz, 4 J =1.5 Hz, 1H, H-5), 6.35 (ddd, J45 = 3.8 Hz, J43 =2.4 Hz, 4 J = 2.0 Hz, 1H, H-4); 13 C- NMR (100 MHz, CDCl3) δ 179.4, 132.8, 126.9, 121.8, (1-(Prop-2-yn-1-yl)-1H-pyrrol-2-yl)ethanone (5b). To a stirred solution of POCl3 (16.2 g, 0.1 mol) and dimethyl acetamide (DMA) (10.44 g, 0.12 mol) in dry ether (100 ml) was added pyrrole (10.0 g, 0.15 mol) dropwise at 0 C. The mixture was stirred at room temperature for 16 h. The reaction mixture was worked up as described above to give the acetyl compound 5b (6.98 g, 63%). 1 S4

5 1-(Prop-2-yn-1-yl)-1H-pyrrole-2-carbaldehyde (6a). To a solution of 1Hpyrrole-carbaldehyde (5a) (10.0 g, mol) in DMF (70 ml), NaH (4.08 g, 0.17 mol) was added slowly at the temperature of an ice-bath. After the completion of addition, the reaction mixture was stirred for 30 min and then propargyl bromide (16.2 g, 0.14 mol) was carefully added dropwise to the solution. The reaction mixture was stirred for h. Extraction with ethyl acetate (3 150 ml) afforded the residue, which was then separated by column chromatography on silica gel eluting with n- hexane/etoac (3:1) to yield 1-(prop-2-yn-1-yl)-1H-pyrrole-2-carbaldehyde (6a) as a light orange liquid (9.94 g, 71%). 2 1 H-NMR (400 MHz, CDCl3) δ 9.55 (d, J = 1.0 Hz, 1H, -CHO), 7.25 Hz (bs, 1H, H-5), 6.95 (dd, J3,4 = 4.0 and J3,5 = 1.7 Hz, 1H, H-3), 6.27 (dd, J45 = 4.0 and J43 = 2.6 Hz, 1H, H-4), 5.20 (d, J = 2.6 Hz, 2H, CH2), 2.46 (t, J = 2.6 Hz, 1H, C CH); 13 C- NMR (100 MHz, CDCl3) δ 179.5, 131.0, 130.3, 124.9, 110.1, 77.4, 74.3, (1-(Prop-2-yn-1-yl)-1H-pyrrol-2-yl)ethanone (6b). To a solution of 2- acetylpyrrolepyrrole 5b (6.98 g, ) in DMF (75 ml) was added NaH (60%, 2.53 g, 0.11 mol) at 0 C portionwise over 1 h. The resulting mixture was stirred at 0 C for 0.5 h, and to the reaction flask was added a solution of propargyl bromide (80% in xylene, g, mol) in DMF (30 ml) dropwise over 0.5 h. The reaction mixture was stirred at room temperature for 16 h, and after adding water (50 ml), the mixture was extracted with EtOAc (4 25 ml). The extracts were washed with brine (4 15 ml), dried over MgSO4, and evaporated. The crude product was chromatographed on silica gel eluting with hexane/etoac (5/1) to give the product 6b as an orange-yellow liquid (6.45 g, isolated yield: 69%; crude yield: 80%). 3 1 H NMR (400 MHz, CDCl3) δ 7.15 (dd, J5,4 = 2.4 and J5,3 = 2.0 Hz, 1H, H-5), 6.94 (dd, J3,4 = 4.0 and J3,5 = 2.0 Hz, 1H, H-3), 6.15 (dd, J4,3 = 4.0 and J4,5 = 2.4 Hz, 1H, H-4), 5.17 (d, J6,8 = 2.6 Hz, 2H, CH2), 2.42 (s, 3H, CH3), 2.39 (t, J8,6 = 2.6 Hz, 1H, H- 8); 13 C NMR (100 MHz, CDCl3) δ 188.5, 130.0, 129.1, 120.5, 108.6, 78.2, 73.9, 38.7, (But-2-yn-1-yl)-1H-pyrrole-2-carbaldehyde (6c). To a solution of 1Hpyrrole-carbaldehyde (5a) (0.700 g, 7.4 mmol) in DMF (10 ml), NaH (0.262 g, 10.9 mmol) was added slowly at temperature of an ice-bath. After the completion of addition, the reaction mixture was stirred for 30 min and then 1- bromobut-2-yne (1.21 g, 9.1 mmol) was carefully added dropwise to the solution. The reaction mixture was stirred for 24 h at room temperature and extracted with EtOAc (3 20 ml. The collected organic phases were washed with brine, water, and dried over MgSO4. Removal of the solvent under the reduced pressure afforded the residue, which was then purified by column S5

6 chromatography on silica gel eluting with n-hexane/etoac (3:1) to yield 1-(but-2-yn-1-yl)- 1H-pyrrole-2-carbaldehyde (6c) as a yellow liquid (0.664 g, 61%). 1 H-NMR (400 MHz, CDCl3) δ 9.5 (bt, J = 1.5 Hz, 1H, CHO), 7.26 (bs, 1H, H-3), 6.93 (dt, J = 4.0 and J = 1.5 Hz, H-5), 6.24 (ddd, J = 4.0, J = 2.6, and J = 1.1 Hz, 1H, H-4), (m, 2H, CH2), 1.84 (bs, 1H, CH3); 13 C-NMR (100 MHz, CDCl3) δ 179.4, 131, 130.3, 124.7, 109.7, 82.3, 72.8, 38.6, 3.5; IR (ATR, cm -1 ) 1653, 1527, 1479, 1403, 1337, 1313, 1281, 1217, 1069, 1028, 741, 605; HRMS calculated for C9H9NO [M+H] + 148,07624; found General procedure for Sonogashira couplings (7a-c and 10a,b). Cuprous iodide (17.05 mg, mmol), triphenylphosphine (89 mg, mmol), palladium acetate (17.05 mg, mmol) and dry diisopropylamine (14 ml, mmol) were added in a solution of aryl halide (6.83 mmol) in dry THF (50 ml) under nitrogen atmosphere. Then 1-(prop-2-yn-1-yl)-1Hpyrrole-2-carbaldehyde (6a) (1.0 g, 7.51 mmol) diluted in dry THF (5 ml) was added to the reaction mixture at room temperature. The mixture was heated at reflux temperature and stirred for 24 h. After cooling, the solvent was removed under the reduced pressure. Water (50 ml) was added to the residue and extracted with ethyl acetate (3 50 ml) and lastly the combined organic layers were washed with brine and water, and dried over MgSO4. Removal of the solvent under the reduced pressure gave the crude product, which was purified by column chromatography on silica gel eluting with hexane/ethyl acetate (3:1) afforded the compounds 7a. 1-(3-Phenylprop-2-ynyl)-1H-pyrrole-2-carbaldehyde (7a): A pale brown solid, mp o C. 1 H-NMR (400 MHz, CDCl3) δ 9.59 (d, J =0.9 Hz, 1H, CHO), (m, 2H, arom.), 7.31 (br s, 1H, H-5), (m, 3H, arom.), 6.92 (dd, J3,4 = 4.0 and J3,5 = 1.7 Hz, 1H, H-3), 6.23 (dd, J4,3 = 4.0 and J4,5= 2.7 Hz, 1H, H-4), 5.43 (s, 1H, CH2); 13 C-NMR (400 MHz, CDCl3) δ 179.5, 131.7, 131.1, 130.4, 128.7, 128.3, 124.9, 122.1, 110.0, 86.0, 82.6, 38.9; IR (ATR, cm - 1 ) 1648, 1637, 1474, 1401, 1355, 1316, 1219, 1075, 1030, 759, 691; HRMS calculated for C14H11NO [M+H] ; found [3-(4-Methoxyphenyl)prop-2-yn-1-yl]-1H-pyrrole-2-carbal-dehyde (7b). 1-(Prop-2-yn- 1-yl)-1H-pyrrole-2-carbaldehyde (6a) (1.0 g, 7.51 mmol) was reactd as described above. Pale yellow solid (1.22 g, 75% isolated yield, crude yield 81%), mp C. 1 H-NMR (400 MHz, CDCl3) δ 9.43 (d, J = 0.9 Hz, 1H, -CHO), (m, 3H, 2 arom. and H-5), 6.82 (dd, J3,4 = 4.0 and J3,5 = 1.7 Hz, 1H, H-3), 6.14 (dd, J4,3 = 4.0 and J4,5 S6

7 = 2.7 Hz, 1H, H-4), 5.25 (s, 1H, CH2), 3.65 (s, 3H, OCH3); 13 C-NMR (400 MHz, CDCl3) δ 179.4, 159.8, 133.1, 131.0, 130.3, 124.8, 114.1, 113.8, 109.8, 86.0, 81.2, 55.1, 38.9; IR (ATR, cm -1 )) 2928, 1604, 1508, 1465, 1298, 1244, 1172, 1075, 1027, 939, 829, 723, 604, 534; HRMS for C15H13NO2 [M+H] + : ; found: [3-(3-Nitrophenyl)prop-2-yn-1-yl]-1H-pyrrole-2-carbaldehyde (7c): Pale yellow powder (0.733 g, 42% isolated yield), mp C. 1 H-NMR (400 MHz, CDCl3) δ 9.59 (d, J = 0.9 Hz, 1H, CHO), 8.26 (bt, J = 1.8 Hz, 1H, arom.), 8.17 (bd, J = 8.3 Hz, 1H, 1H, arom.), 7.73 (bt J = 8.3 Hz 1H, arom.), 7.50 (br t, J = 8.0, 1H, H- ), 7.28 (bs, 1H, H-5), 7.00 (ddd, J3,4 = 4.1, J3,5 = 1.9, and J3,CHO = 0.9 Hz, 1H, H-3), 6.32 (ddd, J4,3 = 4.1, J4,5 = 2.8, and J = 0.7 Hz, 1H, H-4), 5.45 (s, 2H, CH2); 13 C-NMR (400 MHz, CDCl3) δ 179.6, 148.0, 137.4, 131.1, 130.4, 129.4, 126.6, 125.0, 123.9, 123.4, 110.3, 85.7, 83.1, 38.7; IR (ATR, cm -1 ) 1648, 1526, 1473, 1401, 1369, 1348, 1311, 1216, 1073, 904, 874, 805, 770, 732, 671, 606, 522; HRMS calculated for C14H10N2O3 [M-H] ; found Prop-2-ynyl-1H-indole-2-carbaldehyde (9a). To a stirred solution of 1H-indole-2-carbaldehyde (8) 4 (2.64 g, 18.2 mmol) in dry DMF (20 ml), solid NaH was added (0.48 g, 20 mmol) piecewise. After a while, at the end of releasing of H2 gas, propargyl bromide (80 wt. % in toluene) (2.4 ml, 21.8 mmol) was diluted with 1:3 ratio of dry DMF and added to the stirring solution over 30 min. After the completion of the reaction (6 h), water (100 ml) was added and the mixture was extracted with EtOAc (3 30 ml). The collected organic phases were washed with brine, water, and dried over MgSO4. Removal of the solvent gave 9a (2.56 g, 97%) as a pale yellow solid m.p C, (Lit. m.p C). 4 1 H NMR (400 MHz, CDCl3) δ 9.81 (s, 1H, H-8), 7.68 (dt, J4,5 = 8.0 and J4,6 = J4,3 = 0.9 Hz, 1H, H-4), 7.47 (dd, J7,6= 8.4 and J7,5 = 1.0 Hz, 1H, H-7), 7.40 (ddd, J6,7 = 8.4, J6,5 = 7.0 and J6,4 = 0.9 Hz, 1H, H-6), 7.22 (d, J3,4 = 0.9 Hz, 1H, H- 3), 7.15 (ddd, J5,4 = 8.0, J5,6 =7.0 and J5,7 =1.0 Hz, 1H, H-5), 5.39 (d, J = 2.5 Hz, 2H, CH2), 2.20 (t, J1= 2.5 Hz, 1H, C CH). 13 C NMR (100 MHz, CDCl3) δ 182.6, 140.1, 134.5, 127.4, 126.6, 123.5, 121.5, 118.7, 110.8, 78.2, 72.5, IR (ATR, cm -1 ) 3237, 2923, 2851, 1661, 1478, 1461, 1162, 1123, 1110, 757, 728. HRMS calcd for C12H9NO [M+H] + : ; found: S7

8 1-But-2-ynyl-1H-indole-2-carbaldehyde (9b). A stirring solution of indole-2-carbaldehyde (8) (1.45 g, 10 mmol) in dry DMF was added NaH 0,312 g NaH during 30 min. After completion of addition, a solution of 1-bromobut-2-yne (0,96 ml, 11 mmol) in dry DMF (5 ml) was slowly added and stirred for 4 h. Water (50 ml) was added and the resulting solution was extracted with EtOAc (3 50 ml). The collected organic layers were washed with brine and dried over MgSO4. Evaporation of the solvent under the reduced pressure gave the crude product (1.87 g, 95%). The residue was purified by silica gel column chromatography eluting with hexane/etoac (3:1) afforded target product 9b as a pale yellow solid (1.10 g, 56%) from CH2Cl2/n-hexane, m.p o C. 1 H NMR 1 H NMR (400 MHz, CDCl3) δ 9.89 (s, 1H, CHO), 7.75 (bd, J4,5 = 8.1 Hz, 1H, H-4), 7.55 (bd, J7,6 = 8.3 Hz, 1H, H-7), 7.46 (ddd, J6,7 = 8.3 J6,5 = 6.8, and J6,4 = 1.0 Hz, 1H, H-6), 7.28 (bs, 1H, H-3), 7.21 (ddd, J5,4 = 8.0, J5,6 = 6.8, and J5,7=0.7 Hz, 1H, H-5), 5.39 (q, J9,11 = 2.4 Hz, 1H, CH2), 1.75 (t, J11,9 = 2.4 Hz, 1H, CH3). 13 C NMR (100 MHz, CDCl3) δ 182.7, 140.2, 134.6, 127.2, 126.6, 123.5, 121.3, 118.3, 111.1, 80.2, 73.7, 34.3, 3.5. IR (ATR, cm -1 ) 2920, 2851, 1661, 1610, 1478, 1344, 1135, 739. HRMS calcd for C13H11NO [M+H] + : ; found: (3-Phenylprop-2-ynyl)-1H-indole-2-carbaldehyde (10a). 1- Prop-2-ynyl-1H-indole-2-carbal-dehyde (9a) (0.360 g, 1.97 mmol) was reacted with iodobenzene as described above (Sonogashira coupling). The crude product was purified by silica gel column chromatography eluting with hexane/etoac (3:1) to afford the coupling product 10a. Pale yellow needles (440 mg, 86%) from n-hexane(etoac, m.p C. 4 1 H NMR (400 MHz, CDCl3) δ 9.89 (s, 1H, CHO), 7.75 (dt, J4,5= 8.0 and J4,6 = J4,3 = 0.9 Hz, 1H, H-4), 7.62 (dd, J7,6 = 8.4 and J7,5 = 0.9 Hz, 1H, H-7), 7.46 (ddd, J6,7 = 8.4, J6,5 = 7.0, and J6,4 = 0.9 Hz, 1H, H-6), (m, 2H, arom.), 7.28 (d, J3,4= 0.9 Hz, 1H, H-3), (m, 4H, arom.), 5.66 (s, 2H, CH2). 13 C NMR (100 MHz, CDCl3) δ 182.7, 140.3, 134.6, 131.8, 128.4, 128.2, 127.3, 126.7, 123.5, 122.4, 121.5, 118.6, 111.1, 84.2, 83.7, IR (ATR, cm -1 ) 2917, 2849, 1663, 1523, 1459, 1346, 1149, 1127, 731. HRMS calcd for C18H13NO [M+H] + : ; found: S8

9 1-[3-(4-Methoxyphenyl)prop-2-ynyl]-1H-indole-2-carbaldehyde (10b). 5 1-Prop-2-ynyl-1H-indole-2-carbal-dehyde (9a) (0.366 g, 2 mmol) was reacted with 4-iodoanisole as described above (Sonogashira coupling). The crude product was purified by silica gel column chromatography eluting with hexane/etoac (3:1) to afford the coupling product 10b. Pale yellow crystals like snowflakes (505 mg, 87%) from n- hexane/etoac, m.p C, (Lit. m.p. 72 C). 5 1 H NMR (400 MHz, CDCl3) δ 9.82 (s, 1H), 7.67 (dd, J4,5 = 8.0, J4,6 = 1.0 Hz, 1H, H-4), 7.55 (dd, J7,6 = 8.4, J7,5 = 0.9 Hz, 1H, H-7), 7.38 (ddd, J6,7 = 8.4, J6,5 = 7.0, and J6,4 = 0.9 Hz, 1H, H-6), (m, 3H, H-3 and 2 arom.), 7.13 (ddd, J5,4 = 8.0, J5,6 = 7.0, and J5,7 = 0.9 Hz, 1H, H-5), (m, 2H, arom.), 5.57 (s, 2H, CH2), 3.67 (s, 3H, OCH3). 13 C NMR (100 MHz, CDCl3) δ 182.7, 159.7, 140.3, 134.6, 133.3, 127.3, 126.7, 123.5, 121.4, 118.5, 114.5, 113.8, 111.2, 84.1, 82.3, 55.3, IR (ATR, cm -1 ) 2915, 1662, 1605, 1568, 1509, 1250, 844. HRMS calcd for C19H15NO2 [M+H] + : ; found: General procedure for oxime generation (11a-j). A solution of the starting compound 6a-c, 7a-c, 9a,b, or 10a,b (1.0 equiv.) in ethanol (10 ml) was added to the mixture of NH2OH.HCl (2.0 equiv.) and anhydrous Na2CO3 (2.0 equiv.) in ethanol (10 ml). The reaction mixture was heated to 70 C for 6-24 h. After the completion of the reaction, ethanol was removed under the reduced pressure, then H2O (20 ml) was added to the residue. The mixture was extracted with ethyl acetate (3 20 ml). The combined organic layers were washed with brine, water, and dried over MgSO4. Evaporation of the solvent under the reduced pressure gave a mixture of E- and Z-isomers of the corresponding oximes. 11a-j. 1-Prop-2-ynyl-1H-pyrrole-2-carbaldehyde oxime (11a): 1-Prop-2-ynyl- 1H-pyrrole-2-carbaldehyde (6a) (05.g, 3.76 mmol) was reacted with NH2OH HCl and Na2CO3 as described above to yield a mixture of E- and Z-isomers of oxime as a light yellow solid (E-isomer g, 64% and Z- isomer g, 16%. The ratio was calculated from the 1 H-NMR spectrum of the oxime mixture). 1 H-NMR (E-isomer) (400 MHz, CDCl3) δ 8.10 (bs, 1H, OH) 8.11 (s, 1H, CH=N), 6.99 (dd, J5,4 = 2.9 and J5,3= 1.7 Hz, 1H, H-5), 6.45 (dd, J3,4 = 3.7 Hz, J3,5 = 1.7 Hz, 1H, H-3), 6.21 (dd, J4,3 = 3.7 Hz, J4,5 = 2.9 Hz, 1H, H-4), 5.00 (d, J = 2.5 Hz, 2H, CH2), 2.43 (t, J = 2.5 Hz, 1H, C CH); 13 C-NMR (100 MHz, CDCl3) δ 143.2, 125.8, 124.4, 115.7, 109.2, 78.2, 73.7, 38.4; 1 H-NMR (Z-isomer) (400 MHz, CDCl3) δ 8.10 (bs, 1H, OH), 7.56 (s, 1H, -CH=N), 7.37 (dd, J3,4 = 3.9 and J3,5 = 1.6 Hz, 1H, H-3), 6.87 (dd, J5,4 = 2.5 and J5,3 = 1.6 Hz, 1H, H-5), 6.28 S9

10 (dd, J4,5 = 2.5 Hz, J3,4 = 3.9 Hz, 1H, H-4), 4.78 (d, J = 2.5 Hz, 2H, CH2), 2.48 (t, J = 2.5 Hz, 1H, C CH); 13 C-NMR (100 MHz, CDCl3) δ 135.6, 124.6, 122.4, 119.7, 109.6, 77.2, 74.6, 37.0; IR (ATR, cm -1 ) 3225, 1730, 1630, 1047, 1295, 1244, 1078, 933, 818, 725, 665, 504; HRMS calculated for C8H8N2O [M+H] + : ; found: (E)-1-(1-(prop-2-yn-1-yl)-1H-pyrrol-2-yl)ethanone oxime (11b). A solution of 1-(1-(prop-2-yn-1-yl)-1H-pyrrole-2-yl)ethanone (6b) (0.5 g, 3.4 mmol) in ethanol (10 ml) was reacted with NH2OH HCl (6.0 mmol) and NaOAc (7.0 mmol) at reflux temperature for 24 h as described above. After usual work-up the residue was purified by silica gel column chromatography eluting with n- hexane/etoac (3:2) to afford only a single oxime isomer 11b (0.328 g, 60%). Light yellow solid (Decomposition). (E-isomer) 1 H-NMR (400 MHz, CDCl3) δ 8.4 (bs, 1H, OH), 6.71 (bt, J = 1.8 Hz, 1H, H-5), 6.47 (dd, J3,4 = 3.6 and J3,5 = 1.4 Hz, 1H, H-3), 6.21 (bdd, J4,3 = 3.8 and J4,5 = 2.5 Hz, 1H, H-4), 4.94 (bs, 2H, CH2), 2.23 (s, 3H, CH3), 1.26 (bs, 1H, C CH) C NMR (100 MHz, CDCl3) δ 150.9, 128.0, 125.3, 112.9, 107.9, 81.1, 74.5, 13.1, 3.6. IR (ATR, cm - 1 )3280, 1611, 1430, 1325, 1264, 1221, 1090, 985, 919, 732, 639; HRMS for C9H10N2O [M+H] + 163,08714; found (E/Z)-1-(But-2-yn-1-yl)-1H-pyrrole-2-carbaldehyde oxime (11c): 1- (But-2-yn-1-yl)-1H-pyrrole-2-carbaldehyde (6c) (0.3 g, 2.04 mmol) was reacted with NH2OH HCl and Na2CO3 as described above to yield a mixture of E- and Z-isomers of oxime as a light yellow solid g the mixture of E- and Z-isomers of oxime as a light yellow solid (E-isomer g, 81% and Z- isomer g, 15%. The ratio was calculated from the 1 H-NMR spectrum of the oxime mixture). 1 H-NMR (E-isomer) (400 MHz, CDCl3) δ 8.3 (bs, 1H, OH), 8.13 (s, 1H, -CH=N), 6.99 (dd, J5,4 = 2.8 and J5,3 = 1.7 Hz, 1H, H-5), 6.47 (dd, J3,4 = 3.7 Hz, J3,5 = 1.7 Hz, 1H, H-3), 6.19 (dd, J4,3 = 3.7 Hz, J 4,5 = 2.8 Hz, 1H, H-4), 4.55 (q, J = 2.4 Hz, 2H, CH2), 1.85 (t, J = 2.4 Hz, 3H, CH3); 13 C-NMR (100 MHz, CDCl3) δ 143.1, 125.7, 124.3, 115.1, 108.8, 81.7, 73.5, 38.7, 3.5; 1 H-NMR (Z-isomer) (400 MHz, CDCl3) δ 7.58 (s, 1H, CH=N), 7.36 (dd, J3,4 = 3.9 Hz, J3,5 = 1.6 Hz, 1H, H-3), 6.86 (dd, J5,4 = 2.6 Hz, J5,3= 1.7 Hz, 1H, H-5), 6.26 (dd, J4,3 = 3.7 Hz, J4,5 = 2.6 Hz, 1H, H-4), 4.75 (q, J = 2.4 Hz, 2H, -CH2), 1.84 (t, J = 2.4 Hz, 3H, CH3); 13 C- NMR (100 MHz, CDCl3) δ 135.8, 124.5, 122.3, 119.3, 109.1, 82.4, 72.9, 37.5, 3.5; IR (ATR, cm -1 ) 3154, 1470, 1432, 1294, 1205, 1076, 1024, 948, 900, 834, 716, 489, 419; HRMS calculated for C9H10N2O [M+H] + 163,08714; found S10

11 1-(3-Phenylprop-2-ynyl)-1H-pyrrole-2-carbaldehyde oxime (11d): 1-(3- Phenyl)prop-2-ynyl)-1H-pyrrole-2-carbaldehyde oxime (7a) (0.848 g, 4.05 mmol) was reacted with NH2OH HCl and Na2CO3 as described above to yield a mixture of E- and Z-isomers of oxime 11d as a light yellow solid (E-isomer g, 60% and Z-isomer g, 32%. The ratio was calculated from the 1 H-NMR spectrum of the oxime mixture. (E-isomer) 1 H-NMR (400 MHz, CDCl3) δ 8.2 (bs, 1H, OH) 8.16 (s, 1H, -CH=N), (m, 2H, arom.), (m, 3H, arom.), 7.09 (bdd, J5,4 = 2.8 and J5,3= 1.7 Hz, 1H, H-5), 6.49 (dd, J3,4 = 3.7 and J3,5 = 1.7 Hz, 1H, H-3), 6.23 (dd, J4,3 = 3.7 Hz, J4,5 = 2.8 Hz, 1H, H-4), 5.21 (s, 2H, CH2); (Z-isomer) 1 H- NMR (400 MHz, CDCl3) δ 7.66 (s, 1H, CH=N), (m, 2H, arom.), 7.39 (dd, J3,4 = 3.8 and J3,5 = 1.6 Hz, 1H, H-3), (m, 3H, arom.), 6.95 (bdd, J5,4 = 2.8 and J5,3 = 1.6 Hz, 1H, H-5), 6.29 (dd, J4,3 = 3.8 and J5,4 = 2.8 Hz, 1H, H-4), 5.00 (s, 2H, CH2); E- and Z-Isomers 13 C-NMR (100 MHz, CDCl3) δ 143.3, (2C), 128.8, 128.6, 128.3, 128.2, 125.8, (2C), 124.5, 122.3, 121.9, 119.6, 109.4, 109.0, 115.5, 86.0, 85.5, 83.4, 82.5, 39.2, 37.9; IR (ATR, cm -1 ) 3250, 2844, 1637, 1479, 1405, 1328, 1289, 1227, 1128, 1075, 924, 846; HRMS for C14H12N2O [M+H] + : ; found: [3-(4-Methoxyphenyl)prop-2-ynyl]-1H-pyrrole-2-carbaldehyde oxime (11e): 1-[3-(4-Methoxyphenyl)prop-2-ynyl]-1H-pyrrole-2- carbaldehyde (7b) (0.5 g, 2.08 mmol) was reacted with NH2OH HCl and Na2CO3 as described above to yield a mixture of E- and Z-isomers of oxime 11e as a pale yellow solid (E-isomer g, 66% and Z- isomer g, 25%). The ratio was calculated from the 1 H-NMR spectrum of the oxime mixture. (E-isomer) 1 H-NMR (400 MHz, CDCl3) δ 8.15 (s, 1H, CH=N), 7.68 (m, A-part of AAˊBBˊ system, 2H, arom.), 7.08 (bdd, J5,4 = 2.8 and J5,3 = 1.7 Hz, 1H, H-5), 6.83 (m, B-part of AAˊBBˊ system, 2H, arom.), 6.47 (dd, J3,4 = 3.8 and J3,5 = 1.7 Hz, 1H, H-3), 6.21 (dd, J4,3 = 3.7 Hz, J4,5= 2.8 Hz, 1H, H-4), 5.17 (s, 2H, CH2), 3.80 (s, 3H, OCH3); 1 H-NMR (Z-isomer) (400 MHz, CDCl3) δ 7.65 (s, 1H, CH=N), 7.38 (m, A-part of AAˊBBˊ system, 2H, arom.), 7.40 (br dd, J5,4= 2.9 and J5,3 = 1.8 Hz, 1H, H-5), 6.94 (dd, J3,4 =3.7 and J5,3 = 1.8, 1H, H-3), 6.28 (dd, J4,3 = 3.7 and J4,5 = 2.9 Hz, 1H, H-4), 4.97 (s, 2H, CH2), 3.80 (s, 3H, OCH3); E- and Z- Isomers 13 C-NMR (100 MHz, aceton-d6) δ 162.0, 161.9, 143.7, 136.9, , , 127.2, 127.1, 125.6, 125.2, 120.0, 116.3, 116.0, , , 115.9, 110.5, 110.2, 86.6, 86.2, 84.9, S11

12 84.5, 56.6, 40.3, 39.0, 31.6; IR (ATR, cm -1 ) 2928, 1604, 1508, 1465, 1289, 1244, 1172, 1075, 1027, 939, 829, 723, 604, 534; HRMS calculated for C15H14N2O2 [M+H] ; found [3-(3-Nitrophenyl)prop-2-ynyl]-1H-pyrrole-2-carbaldehyde oxime (11f): 1-[3-(3-Nitrophenyl)prop-2-ynyl]-1H-pyrrole-2-carbaldehyde (7c) (0.733 g, 2.87 mmol) was reacted with NH2OH HCl and Na2CO3 as described above to yield a mixture of E- and Z-isomers of oxime 11f as a pale yellow solid (E-isomer g, 69% and Z-isomer g, 21%). The ratio was calculated from the 1 H-NMR spectrum of the oxime mixture. (E-isomer) 1 H- NMR (E-isomer) (400 MHz, CDCl3) δ 8.27 (bs, 1H, -CH=N), 8.17 (m, 1H, arom.), 8.12 (m, 1H), 7.72 (m, 1H), 7.49 (m, 1H), 7.02 (bs, 1H, H-5), 6.45 (dd, J3,4 = 3.7 and J3,5 = 1.6 Hz, 1H, H-3), 6.23 (dd, J4,3 = 3.7 and J3,5 = 1.6 Hz, 1H, H-4), 5.27 (s, 2H, CH2); (Z-isomer) 1 H-NMR (400 MHz, CDCl3) δ 8.26 (bs, 1H, CH=N), 8.18 (m, 1H), 7.72 (m, 1H), 7.50 (m, 1H), 7.44 (br s, 1H, H-5), 7.01 (bs, 1H, H-3), 6.34 (bt J = 3.0 Hz 1H, H-4), 5.07 (s, 2H, -CH2); 13 C-NMR (100 MHz, aceton-d6) δ 150.2, 143.7, 139.4, 139.4, 136.7, 132.0, 131.9, 128.0, 127.9, 127.5, 127.4, 126.5, 126.0, 125.7, 125.4, 125.2, 125.1, 120.6, 116.3, (2C), 89.4, 88.6, 84.3, 83.7, 40.3, 38.9; IR (ATR, cm -1 ) 3080, 1646, 1527, 1451, 1390, 1346, 1099, 932, 899, 871, 834, 784, 734, 670, 531, 408; HRMS for C14H11N3O3 [M+H] + : ; found: (E/Z)-1-(1-prop-2-ynyl-1H-indol-2-yl)ethanone oxime (11g). A solution of the propargyl aldehyde (9a) (2,13 g, 11,63 mmol) in ethanol (20 ml) was reacted with NH2OH. HCl (750 mg, mmol) and anhydrous Na2CO3 (616 mg, 5.8 mmol) in EtOH (10 ml) at reflux temperature for 4 h as described above. Evaporation of the solvent under the reduced pressure gave a mixture of E- and Z-isomers of the oxime 11g. The 1 H NMR spectral analysis showed the formation of an oxime mixture (93%) consisting of a mixture of E- and Z- isomers (11g) in a ratio of 5:1. The E-isomer was separated by column chromatography on silica gel eluting with hexane/etoac (3:1). Pale yellow solid, m.p C. E-Isomer. 1 H NMR (400 MHz, CDCl3) δ 8.19 (s, 1H, H-8), 7.54 (bd, J4,5 = 8.0 Hz, 1H, H-4), 7.36 (dd, J7,6 = 8.3 Hz, and J7,5 = 1.0 Hz, 1H, H-7), 7.25 (ddd, J6,7 = 8.3, J6,5 = 7.1, and J6,4 = 1.0 Hz, 1H, H-6), 7.07 (ddd, J5,4 = 8.0, J5,6 = 7.1, and J5,7 = 1.0 Hz, 1H, H-5), 6.67 (bs, 1H, H-3), 5.21 (d, J9,11 = 2.5 Hz, 2H, CH2), 2.19 (t, J11,9 = 2.5 Hz, 1H, C CH). 13 C-NMR (100 MHz, CDCl3) δ 144.2, 139.0, 130.3, 127.6, 124.3, 121.7, 120.7, 109.9, 109.4, 78.7, 72.1, IR (ATR, cm -1 ) 3383, S12

13 3253, 1609, 1456, 1163, 1150, 950, 938, 750. HRMS calcd for C12H10N2O [M+H] + : ; found: But-2-ynyl-1H-indole-2-carboxaldehyde oxime (11h). A solution of the methylpropargyl aldehyde (9b) (1.97 g, 10.0 mmol) in ethanol (20 ml) was reacted with NH2OH.HCl (644 mg, 10.0 mmol) and anhydrous Na2CO3 (530 mg, 5.0 mmol) in EtOH (10 ml) at reflux temperature for 6 h as described above. Evaporation of the solvent under the reduced pressure gave a mixture of E- and Z-isomers of the oxime 5. The 1 H NMR spectral analysis showed the formation of an oxime mixture (1.98 g, 93%) consisting of a mixture of E- and Z- isomers in a ratio of 94/4. The E-isomer 11h was separated by column chromatography on silica gel eluting with hexane/etoac (3:1). Pale yellow solid, m.p C. E-Isomer (Isolated yield 66%). 1 H NMR (400 MHz, CDCl3) δ 8.26 (s, 1H, H-8), 7.62 (bd, J4,5 = 8.0 Hz, 1H, H-4), 7.46 (bd, J7,6 = 8.2 Hz, 1H, H-7), 7.32 (ddd, J6,7 = 8.2, J6,5 = 7.2, and J6,4 = 1.1 Hz, 1H, H-6), 7.14 (ddd, J5,4 = 8.0, J5,6 = 7.2, and J5,7 = 0.8 Hz, 1H, H-5), 6.74 (s, 1H, H-3), 5.26 (q, 5 J = 2.3 Hz, 2H, CH2), 1.76 (t, 5 J = 2.3 Hz, 3H, CH3). 13 C NMR (100 MHz, CDCl3) δ 144.0, 138.9, 130.3, 127.5, 124.0, 121.5, 120.5, 110.1, 108.6, 80.1, 74.0, 34.9, IR (ATR, cm -1 ) 3200, 2953, 2921, 1456, 947, 803, 737, 639. HRMS calcd for C13H12N2O [M+H] + : ; found: (3-Phenylprop-2-ynyl)-1H-indole-2-carbaldehyde oxime (11i). A solution phenylpropargyl aldehyde 10a (0.9 g, 3.47 mmol) in ethanol (30 ml) was reacted with NH2OH HCl (224 mg, 3.47 mmol) and anhydrous Na2CO3 (183 mg, 1.74 mmol) at reflux temperature for 4 h as described above. Evaporation of the solvent under the reduced pressure gave a mixture of E- and Z-isomers of the oxime 11i (917 mg (96%), in a ratio of 84/16. The E-isomer 11i was separated by column chromatography eluting with hexane/etoac (3:1) as a pale yellow solid, 505 mg (53%), m.p C. E- Oxime: 1 H NMR (400 MHz, CDCl3) δ 8.30 (s, 1H, H-8), 8.02 (bs, 1H, OH), 7.61 (bd, J4,5 = 8.0 Hz, 1H, H-4), 7.50 (bd, J7,6 = 8.2 Hz, 1H, H-7), 7.35 (dd, J13,14 = 7.5 and J13,15 = 2.0 Hz, 2H, H- 13), 7.30 (ddd, J6,7 = 8.2, J6,5 = 7.1, and J6,4 = 1.1 Hz, 1H, H-6), (m, 3H, H-14 and H-15), 7.14 (ddd, J5,4 = 8.0, J5,6 = 7.1, and J5,7 = 0.8 Hz, 1H, H-5), 6.76 (s, 1H, H-3), 5.47 (s, 2H, H-9). 13 C NMR (100 MHz, CDCl3) δ 144.1, 139.1, 131.8, 130.4, 128.4, 128.2, 127.6, S13

14 124.1, 122.5, 121.5, 120.6, 110.1, 109.0, 84.1, 77.0, IR (ATR, cm -1 ) 3305, 3054, 1441, 1313, 1254, 957, 750. HRMS calcd for C18H14N2O [M+H] + : ; found: [3-(4-Methoxyphenyl)prop-2-ynyl]-1H-indole-2- carbaldehyde oxime (11j). A solution methoxyphenylpropargyl aldehyde 10b (0.349 g, 1.21 mmol) in ethanol (20 ml) was reacted with NH2OH HCl (80 mg, 1.24 mmol) and anhydrous Na2CO3 (183 mg, 0.62 mmol) at reflux temperature for 4 h as described above. Evaporation of the solvent under the reduced pressure gave a mixture of E- and Z-isomers of the oxime 11j (302 mg (82%), in a ratio of 87/13. The E-isomer 11j was separated by column chromatography eluting with hexane/etoac (3:1) to give a pale yellow solid, (164 mg, 45%), m.p C. E-Oxime: 1 H NMR (400 MHz, CDCl3) δ 8.29 (s, 1H, H-8), 7.63 (bd, J4,5 = 7.9 Hz, 1H, H-4), 7.55 (bd, J7,6 = 7.9 Hz, 1H, H-7), 7.33 (ddd, J6,7 = 7.9, J6,5 = 7.5, and J6,4 = 1.1 Hz, 1H, H-6), 7.30 (bd, J13,14 = 9.0 Hz, 2H, H-13), 7.15 (ddd, J5,4 = 7.9, J5,6 = 7.5, and J5,7 = 0.9 Hz, 1H, H-5), 6.78 (d, J14,13 = 9.0 Hz, 2H, H-14), 6.76 (s, 1H, H-3), 5.53 (s, 2H, CH2), 3.78 (s, 3H, OCH3). 13 C NMR (100 MHz, CDCl3) δ 159.7, 143.9, 139.0, 133.4, 130.6, 127.7, 124.1, 121.6, 120.7, 114.6, 113.9, 110.2, 108.5, 84.2, 82.8, 55.3, IR(ATR, cm -1 ) 3250, 2922, 2852, 1598, 1455, 1246, 1170, 742. HRMS calcd for C19H16N2O2 [M+H] + : ; found: General procedure gold-catalyzed cyclization of oxime. A mixture of E/Z-oxime isomers 11 (1 mmol) was dissolved in CHCl3 (3 ml) and AuCl3 (3 mol %) was added to this solution. The reaction mixture was stirred at room temperature for h. The solvent was evaporated under the reduced pressure to give the crude product. The residue was purified by silica gel column chromatography eluting with EtOAc. 3-Methylpyrrolo[1,2-a]pyrazine 2-oxide (12a): A mixture of E/Z-oxime isomers 11a (100 mg, mmol) in CHCl3 (3 ml) and AuCl3 (6.1 g, 3 mol%) was reacted as described above. The residue was chromatographed on a short silica gel column eluting with EtOAc. Colorless crystals (97 mg, 97%) from chloroform, mp C. 1 H-NMR (400 MHz, CDCl3) δ 8.74 (bs, 1H, CH=N), 7.65 (bq, J = 0.7 Hz, 1H, 1H, C=CH), (m, 1H, H-6), 6.81 (dd, J7,8 = 4.1 and J7,6 = 2.5 Hz, 1H, H- 7), 6.73 (bd, J = 4.1 Hz, 1H, H-8), 2.40 (d, J = 0.9 Hz, 3H, CH3). 13 C-NMR (400 MHz, CDCl3) δ 144.4, 135.2, 127.4, 114.8, 114.5, 114.2, 103.0, IR (ATR) 1629, 1302, 1036, 926, 721, 421. HRMS calculated for C8H8N2 [M+H] + : ; found: S14

15 1,3-Dimethylpyrrolo[1,2-a]pyrazine 2-oxide (12b). A mixture of E/Z-oxime isomers 11b (80 mg, 0.49 mmol) in CHCl3 (3 ml) and AuCl3 (4.0 mg) was reacted as described above. The residue was chromatographed on a short basic alumina column eluting with EtOAc. Pale yellow solid (54 mg, 67%), mp C. 1 H-NMR (400 MHz, CDCl3) δ 7.68 (bs, 1H, H-4), 7.23 (dd, J6,7 = 2.5 and J6,8 = 1.2 Hz, 1H, H-6), 6.81 (dd, J7,8 = 4.1 and J7,6 = 2.5 Hz, 1H, H-7), 6.56 (bd, J= 4.1 Hz, 1H, H-8), 2.66 (s, 3H, CH3), 2.43 (d, J = 1.0 Hz 3H, CH3). 13 C-NMR (400 MHz, CDCl3) δ 139.1, 131,1, 128.0, 116.9, 115.7, 114.8, 102.6, 15.0, IR (ATR, cm -1 ) 1496, 1450, 1292, 1188, 1145, 1087, 781, 739; HRMS for C9H10N2O [M+H] ; found Methylpyrazino[1,2-a]indole 2-oxide (12c). A solution of 11g (140 mg, 0.7 mmol) in chloroform (10 ml) was reacted with AuCl3 (3% mmol) as described above. The residue was purified by silica gel column chromatograpy eluting with EtOAc/EtOH (90:10). 12c (37 mg, 26%) was isolated as pale brown solid, m.p C. 1 H-NMR (400 MHz, CDCl3) δ 8.60 (s, 1H), 8.10 (s, 1H), (m, 2H, arom.), (m, 2H, arom.), 6.81 (s, 1H), 2.48 (s, 3H, CH3). 13 C-NMR (100 MHz, CDCl3) δ 171.8, 129.8, 128.7, 123.9, 122.4, 121.5, 117.6, 110.1, 100.0, 94.2, 83.0, IR (ATR, cm -1 ) 2919, 2849, 1466, 1176, 742, 671. HRMS calcd for C12H10N2O [M+H] + : ; found: General procedure for oxime-oxime transformation reactions (13a-g). Starting material 11c-f and 11h (2.0 mmol) was dissolved in CHCl3 (5 ml). AuCl3 (3 mol%) was added in this solution and the reaction mixture was stirred for 24 h at room temperature. Evaporation of the solvent under reduced pressure gave the residue. Mixture of E/Z-isomers of 13a-e was purified with column chromatography on silica gel eluted with indicated solvent systems below. 1-[3E/Z-(hydroxyimino)butyl]-1H-pyrrole-2-carbaldehyde (13a). A mixture of E/Z-oxime isomers 11c (100 mg, 0.62 mmol) in CHCl3 (2 ml) and AuCl3 (2.0 mg) was reacted as described above. The residue was chromatographed on a short silica gel column eluting with n-hexane/etoac (5:1, 3:1, and 2:1) to afford E/Z-isomers purified with column chromatography eluting with 5:1, 3:1, 2:1 hexane:ethyl acetate, which afforded E/Z-isomers as a dark brown oil (60 mg, 54%). E-isomer (41.4 mg 37%) 1 H-NMR (400 MHz, CDCl3) δ 9.51 (s, 1H, CHO), (bs, 1H, OH), (m, 2H), (m, 1H), 4.48 (t, J = 7.2 Hz, 2H, CH2), 2.64 (t, J = 7.2 Hz, 2H, CH2), 1.88 (s, 3H, CH3); 13 C-NMR (101 MHz, CDCl3) δ 179.5, 155.8, 131.8, 131.2, 125.4, 125.4, 110.0, 46.4, 37.5, Z-isomer (18.6 mg 16%). 1 H- S15

16 NMR (400 MHz, CDCl3) δ 9.53 (s, 1H, CHO), 8.58 (s, 1H, CH=N), (m, 2H), (m, 1H), 4.53 (t, J = 7.0 Hz, 2H, CH2), 2.80 (t, J = 7.0 Hz, 2H, CH2), 1.66 (s, 3H, CH3). 13 C-NMR (100 MHz, CDCl3) δ 179.5, 156.3, 131.9, 131.2, 125.4, 109.9, 45.2, 31.4, IR (ATR, cm -1 ) 3253, 1636, 1479, 1401, 1364, 1321, 1080, 1054, 950, 745; HRMS calculated for C9H12N2O2 [M+H] + : 181,09770; found: [(3E/Z)-3-(Hydroxyimino)-3-phenylpropyl]-1H-pyrrole-2-carbaldehyde (13b). A mixture of E/Z-oxime isomers 11d (449 mg, 2.0 mmol) in CHCl3 (5 ml) and AuCl3 (20 mg) was reacted as described above. The residue was chromatographed on a short silica gel column eluting with n- hexane/etoac (3:1) to afford E/Z-isomers of 13b as pale yellow solid. E- isomer (412 mg 85%). 1 H-NMR (400 MHz, CDCl3) δ 9.56 (bs, 1H, CHO), (m, 2H), (m, 3H), (m, 2H), 6.15 (dd, J4,3 = 3.8 Hz, J4,5 = 2.7 Hz, 1H, H-4), 4.64 (t, J = 7.1 Hz, 2H, CH2), 3.29 (t, J = 7.1 Hz, 2H, CH2). 13 C-NMR (100 MHz, CDCl3) δ 179.4, 157.0, 134.9, 131.9, 131.2, 129.6, 128.6, 126.2, 125.1, 109.8, 45.6, 29.0; Z- isomer (15 mg, 3%). 1 H-NMR (400 MHz, CDCl3) δ 9.52 (s,1h, CHO), (m, 2H), (m, 3H), (m, 2H), 6.19 (dd, J4,3 = 4.0 and J4,5 = 2.5 Hz, 1H, H-3), 4.51 (t, J = 7.1 Hz, 2H, CH2), 3.09 (7.1 Hz). IR (ATR, cm -1 ) 3063, 1659, 1480, 1403, 1362, 1321, 1213, 1068, 1026, 937, 743, 681, 609, 466; 1-[(3E/Z)-3-(Hydroxyimino)-3-(4-methoxyphenyl)propyl]-1H-pyrrole-2- carbaldehyde (13c). A mixture of E/Z-oxime isomers 11e (228 mg, 2.0 mmol) in CHCl3 (5 ml) and AuCl3 (8 mg) was reacted as described above. The residue was chromatographed on a short silica gel column eluting with n-hexane/etoac (3:1) to afford E/Z-isomers of 13c as pale yellow solid. E- isomer (95 mg 39%). 1 H-NMR (400 MHz, CDCl3) δ 9.55 (s, 1H, CHO), (m, 2H, arom.), (m, 4H, 2 arom. H-3 and H-5), 6.15 (dd, J4,3 = 4.0 and J4,5 = 2.5 Hz, 1H, H-4), 4.61 (t, J = 7.2 Hz, 2H, CH2), 3.80 (s, 3H, OCH3), 3.24 (t, J = 7.2 Hz, 2H, CH2). 13 C-NMR (100 MHz, CDCl3) δ 179.3, 160.5, 156.1, 133.0, 131.9, 127.7, 127.5, 125.4, 113.9, 109.5, 55.4, 45.7, Z-isomer (91 mg 37%). 1 H-NMR (400 MHz, CDCl3) δ 9.53 (s, 1H, CHO), (m, 2H, arom.), 7.14 (bs, 1H, H-5), (m, 3H, 2 arom. H-3), 6.18 (dd, J4,3 = 4.0 and J4,5 = 2.6 Hz, 1H, H-4), 4.71 (t, J = 7.4 Hz, 2H, CH2), 3.84 (s, 3H, OCH3), 3.43 (t, J = 7.4 Hz, 2H, CH2). 13 C-NMR (100 MHz, CDCl3) δ 179.3, 163.7, 131.1, 131.0, 130.4, 129.6, 127.3, 113.7, 109.8, 55.2, 44.3, IR (ATR, cm -1 ) 3200, 2838, 1654, 1598, 1512, S16

17 1402, 1364, 1320, 1249, 1169, 1077, 1027, 832, 745, 594; HRMS for C15H16N2O3 [M+H] + : Found: [(3E/Z)-3-(Hydroxyimino)-3-(3-nitrophenyl)propyl]-1H-pyrrole-2- carbaldehyde (13d): A mixture of E/Z-oxime isomers 11f (134 mg, 2.0 mmol) in CHCl3 (2 ml) and AuCl3 (3 mg) was reacted as described above. The residue was chromatographed on a short silica gel column eluting with n-hexane/etoac (2:1) to afford E/Z-isomers of 13d as pale yellow solid. 1 H-NMR E-isomer (105 mg, 73%) (400 MHz, CDCl3) δ 9.55 (s, 1H, CHO), 8.87 (bs, 1H, C=NOH), 8.30 (bs, 1H, arom.), 8.15 (dd, J = 8.2 and 1.4 Hz, 1H, arom.), 7.90 (bd, J = 7.8 Hz, 1H, arom.), 7.49 (bt, J = 8.0 Hz, 1H, arom.), (m, 2H), 6.12 (bt, J = 3.2 Hz, 1H, H-4), 4.65 (t, J = 7.0 Hz, 2H, CH2), 3.31 (t, J = 7.0 Hz, 2H, CH2); 13 C-NMR (100 MHz, CDCl3) δ 179.7, 155.0, 137.0, 132.0, 131.8, 131.1, 129.4, 126.0, 125.5, 123.8, 121.0, 110.1, 45.5, 28.5; Z-isomer 1 H-NMR (400 MHz, CDCl3) δ 9.49 (s, 1H, CHO), 8.87 (bs, 1H, C=NOH), 8.30 (bs, 1H, arom.), 8.21 (bd, J = 8.1 Hz, 1H, arom.), 7.80 (bd, J = 8.0 Hz, 1H, arom.), 7.58 (bt, J = 8.0 Hz, 1H, arom.), (m, 2H), 6.19 (bt, J = 3.3 Hz, 1H, H-4), 4.54 (t, J = 7.1 Hz, 2H, CH2), 3.1 (t, J = 7.1 Hz, 2H, CH2); IR (ATR, cm -1 ) , 2920, 1625, 1524, 1476, 1401, 1343, 1077, 1030, 966, 733, 678, 605; HRMS calculated for C14H13N3O4 [M-H] - : ; found: [(3E/Z)-3-(hydroxyimino)butyl]-1H-indole-2-carbaldehyde (13e). A mixture of E/Z-oxime isomers 11h 126 mg (0.6 mmol) in CHCl3 (2 ml) and AuCl3 (3 mg) was reacted as described above to give an inseparable mixture of E/Z-isomers of 13e (22%) in a ratio of 62:38. E- Isomer: 1 H NMR (400 MHz, CDCl3) δ 9.88 (s, 1H, CHO), 7.74 (bd, J4,5 = 8.0 Hz, 1H, H-4), 7.54 (bd, J7,6 = 8.3 Hz, 1H, H-7), (m, 1H, H-6), 7.29 (s, 1H, H-3), 7.17 (ddd, J5,4 = 8.0, J5,6 = 6.0, and J5,7 = 1.5 Hz, 1H, H-5), 4.75 (quasi t, A-part of A2X2-system, 2H, CH2), 2.68 (quasi t, B-part of A2X2-system, 2H, CH2), 1.94 (s, 3H, CH3); Z-Isomer: 1 H NMR (400 MHz, CDCl3) δ 9.89 (s, 1H, CHO), 7.73 (bd, J4,5 = 8.0 Hz, 1H, H-4), 7.44 (bd, J7-6 = 8.1 Hz, 1H, H- 7), (m, 1H, H-6), 7.43 (s, 1H, H-3), 7.17 (ddd, J5,4 = 8.0, J5,6 = 6.0, and J5,7 = 1.5 Hz, 1H, H-5), 4.77 (quasi t, A-part of A2X2-system, 2H, CH2), 2.84 (quasi t, B-part of A2X2-system, 2H, CH2), 1.81 (s, 3H, CH3). IR (ATR, cm -1 ) 3267, 2919, 2849, 1708, 1664, 1611, 1518, 1461, 1412, 1354, 1315, 1259, 1162, 1127, 1112, 1078, 1014, 962, 845, 797, 737, 648, 588. HRMS calcd for C13H14N2O2 [M+H] + : 231,1170; found: 231,1128. S17

18 1-[(3E/Z)-3-(hydroxyimino)-3-phenylpropyl]-1H-indole-2- carbaldehyde (13f). A mixture of E/Z-oxime isomers 11i (80 mg, 0.3 mmol) in CHCl3 (15 ml) and HAuCl4 2H2O (4.0 mg, 3% mmol) was reacted as described above. The residue was chromatographed on a short silica gel column eluting with n-hexane/etoac (3:1) to afford E/Z-isomers 42 mg (49%) in a ratio of 80/20. E-Isomer (13f). 1 H NMR (400 MHz, CDCl3) δ 9.89 (s, 1H, H-8), (m, 3H, H-4 and H-13), 7.59 (dd, J7,5 = 8.4, and J7,6 =0.8 Hz, 1H, H-7), 7.42 (ddd, J6,7 = 8.4, J6,5 = 7.0, and J6,4 = 1.2 Hz, 1H, H- 6), (m, 3H, H-14 and H-15), 7.24 (d, J3,4 = 0.5 Hz, 1H, H-3), 7.17 (ddd, J5,4 = 8.0, J5-6 = 7.0, and J5, 7 = 0.8 Hz, 1H, H-5), 4.86 (bt, J9,10 = 7.8 Hz, 2H, H-9), 3.30 (t, J10,9 = 7.8 Hz, 2H, H-10). 13 C NMR (100 MHz, CDCl3) δ 182.6, 157.0, 140.4, 135.1, 131.8, 129.4, 128.5, 127.2, 126.4, 126.2, 123.3, 121.1, 118.2, 110.9, 41.3, IR (ATR, cm -1 ) 3283, 3054, 1643, 1456, 1313, 955, 748. HRMS calcd for C18H16N2O2 [M+H] + : ; found: [(3Z)-3-(hydroxyimino)-3-(4-methoxyphenyl)propyl]- 1H-indole-2-carbaldehyde (13g): A mixture of E/Z-oxime isomers 11j (180 mg, 0.6 mmol) in CHCl3 (15 ml) and HAuCl4 2H2O (3% mmol) was reacted as described above. The residue was chromatographed on a short silica gel column eluting with n-hexane/etoac (3:1) to afford a mixture of E/Z-isomers of corresponding oxime (67 mg, 35%) as a pale brown solid in a ratio of 77/23 of E- and Z-isomers. E-Isomer (13g): 1 H NMR (400 MHz, CDCl3) δ 9.86 (s, 1H, CHO), 7.71 (bd, J4,5 = 8.0 Hz, 1H, H-4), 7.67 (bd, J7-,6 = 8.5 Hz, 1H, H-7), 7.51 (d, J =8.9 Hz, 2H, arom.), 7.39 (ddd, J6,7 = 8.5, J6,5 = 6.8, and J6,4 = 1.1 Hz, 1H, H-6), 7.25 (d, J3,4 = 0.6 Hz, 1H, H-3), 7.17 (ddd, J5,4 = 8.0, J5,6 = 6.8, and J5,7 = 1.0 Hz, 1H, H-5), 6.91 (d, J = 8.9 Hz, 2H, arom.), 4.74 (quasi t, A-part of A2X2-system, 2H, CH2), 3.83 (s, 3H, H-16), 3.03 (quasi t, B- part of A2X2-system, 2H, CH2). 13 C NMR (100 MHz, CDCl3) δ 182.9, 168.4, 130.7, 127.7, 126.3, 123.5, 122.0, 121.9, 121.4, 120.6, 119.1, 114.1, 114.1, 110.8, 100.0, 55.5, 42.3, IR (ATR, cm -1 ) 3300, 2918, 2849, 1667, 1599, 1509, 1250, 1167, 1027, 741. HRMS calcd for C19H18N2O3 [M+H] + : ; found: S18

19 1-{(3E/Z)-3-[(acetyloxy)imino]-3-phenylpropyl}-1H-pyrrole-2- carbaldehyde (14). A mixture of oximes 13b (72 mg, 0.29 mmol) was successively dissolved in pyridine (5 ml) and then acetic anhydride (88 mg, 0.87 mmol) was added to the solution. The reaction mixture was stirred overnight at room temperature. Then H2O (10 ml) was added and extracted with ethyl acetate (3 10 ml). The combined organic layers were washed with 2M HCl, 5% NaHCO3, and water, and dried over MgSO4. Removal of the solvent under the reduced pressure gave 17 as a yellow viscous liquid (52 mg, 62%). E-isomer 1 H-NMR (400 MHz, CDCl3) δ 9.54 (bs, 1H, CHO), (m, 2H, arom.), (m, 3H, arom.), 6.90 (dd, J3,4 = 4.0 and J3,5 = 1.7 Hz, 1H, H-3), 6.77 (bs, 1H, H-5), 6.14 (dd, J4,3 = 4.0 Hz, J4,5 = 2.5 Hz, 1H, H-4), 4.53 (t, J = 6.9 Hz, CH2), 3.34 (t, J = 6.9 Hz, CH2), 2.21 (s, 3H, CH3). 13 C-NMR (100 MHz) δ 179.2, 168.4, 162.6, 133.2, 131.5, 131.1, 130.1, 128.6, 127.1, 125.2, 109.9, 46.0, 30.0, 19.6; IR (ATR, cm -1 ) 1764, 1654, 1479, 1404, 1365, 1321, 1195, 997, 930, 748, 693, 607; HRMS calculated for C16H16N2O3 [M+Na] + : ; found [3-(4-methoxyphenyl)-3-oxopropyl]-1H-pyrrole-2-carbaldehyde (15). Mercuric sulfate (1 mole %), 5 drops of sulfuric acid, methanol (70%, 15 ml), acetone (70%, 15 ml), and acetic acid (60%, 15 ml) were placed in flask equipped with a reflux condenser. The mixture was kept at 60 C and alkyne 7b (479 mg, 2 mmol) was added, with good stirring, over a period of one hour. The reaction mixture was then stirred at 60 C for an hour. After cooling to room temperature, the solvent was evaporated and the residue was filtered through a short silica gel column eluing with n-hexane/etoac (5:1) to give the ketoaldehyde 15. White solid in quantitative yield (515 mg, 100%), mp C. 1 H-NMR (400 MHz, CDCl3) δ 9.53 (d, J = 0.8 Hz, 1H, CHO), (m, A-part of AAˊBBˊ system, 2H, arom.), 7.14 (bs, 1H, H-5), 6.93 (dd, J = 4.0 and J = 1.7 Hz, 1H, H-3), (m, B-part of AAˊBBˊ system, 2H, arom.), 6.18 (dd, J = 4.0 and J = 2.5 Hz, 1H, H-4), 4.70 (t, J = 6.4 Hz, 2H, CH2), 3.84 (s, 3H, OCH3), 3.42 (t, J = 6.4 Hz, 2H, CH2); 13 C-NMR (100 MHz, CDCl3) δ 196.3, 179.4, 163.8, 133.1, 131.2, 130.5, 129.8, 125.5, 113.9, 109.7, 55.6, 44.5, 39.5; IR (ATR, cm -1 ) 2945, 2849, 1655, 1601, 1576, 1365, 1313, 1248, 1176, 979, 842, 748, 599; HRMS calculated for C15H15NO3[M+H] ; found S19

20 3-[2-(1,3-dithian-2-yl)-1H-pyrrol-1-yl]-1-(4-methoxyphenyl)- propan -1-one (16). A mixture ketoaldehyde 15 (107 mg, 0.42 mmol), 1,2-ethanedithiol (35µL, 0,42 mmol) and SnCl2 2H2O (10 mg, 10 mol %) in 3 ml ether was stirred for 3 h. After completion of the reaction the residue was crystallized from ether in a refrigerator to give the thioketal 16. White crystals (100 mg, 71%), mp C. 1 H-NMR (400 MHz, CDCl3) δ (m, A-part of AAˊBBˊ system, 2H, arom.), (m, B-part of AAˊBBˊ system, 2H, arom.), 6.71 (dd, J = 2.5 and 1.8 Hz, 1H, H-5), 6.29 (dd, J = 3.5 and 1.8 Hz, 1H, H-3), 6.06 (dd, J = 3.5 and J = 2.5 Hz, 1H), 5.85 (s, 1H), 4.47 (t, J = 7.3, 2H, CH2), 3.87 (s, 3H, OCH3), 3.48 (t, J = 7.3, 2H, CH2), 3.48 t, J = 7.2 Hz, 2H, CH2) (m, 2H, SCH2), (m, 2H, SCH2); 13 C-NMR (100 MHz, CDCl3) δ 196.2, 163.9, 130.5, 129.7, 129.0, 123.0, 114.0, 109.6, 107.7, 55.6, 48.3, 42.0, 40.3, IR (ATR, cm -1 ) 2912, 1669, 1592, 1509, 1315, 1260, 1166, 1014, 986, 842, 752, 709, 586; HRMS calculated for C17H19NO2S2 [M+H] ; found (1E/Z)-3-[2-(1,3-dithian-2-yl)-1H-pyrrol-1-yl]-1-(4-methoxyphenyl)propan-1-one oxime (17). To the mixture of NH2OH.HCl (23.0 mg, mmol) and anhydrous Na2CO3 (35.6 mg, mmol) in EtOH (3 ml), a solution of thioketal 16 (56.0 mg, mmol) in EtOH (1 ml) was added. The reaction mixture was heated to C for 7-8 h. After completion of reaction, the mixture was filtered and the filtrate was evaporated to give oxime as white solid (58.5 mg, 100 %). E-Isomer 17: 1 H-NMR (400 MHz, CD3COCD3) δ (s, 1H), (m, A-part of AAˊBBˊ system, 2H, arom.), (m, B-part of AAˊBBˊ system, 2H, arom.), 6.76 (dd, J5,4 = 2.6 and J5,3 = 1.8 Hz, 1H, H-5), 6.19 (dd, J3,4 = 3.5 and J3,5 = 1.8 Hz, 1H H-3), 5.95 (s, 1H), 5.92 (bt, J = 3.1 Hz, 1H, H-4), 4.29 (t, J = 7.7 Hz, 2H, CH2), 3.81 (s, 3H OCH3), (m, 2H, SCH2), (m, 2H, SCH2), 3.24 (t, J = 7.7 Hz, 2H, CH2). 13 C-NMR (100 MHz, CD3COCD3) δ 162.4, 156.4, 131.2, 130.5, 129.4, 124.3, 115.6, 111.0, 109.1, 56.7, 49.6, 45.0, 40.8, Z-Isomer 17: 1 H-NMR (400 MHz, CD3COCD3) δ 9.95 (s, 1H), (m, A-part of AAˊBBˊ system, 2H, arom.) (m, B-part of AAˊBBˊ system, 2H, arom.), 6.76 (dd, J5,4 = 2.6 and J5,3 = 1.8 Hz, 1H, H-5), 6.12 (dd, J3,4 = 3.5 and J3,5 = 1.8 Hz, 1H, H-3), 5.92 (t, J = 3.1 Hz, 1H, H-4), 5.82 (s, 1H, CH), 4.22 (t, J = 7.7 Hz, 2H, CH2), 3.83 (s, 3H, OCH3), (m, 2H, SCH2), (m, 2H, SCH2), 3.04 (t, J = 7.7 Hz, 2H, CH2). 13 C-NMR (100 MHz, CD3COCD3) δ 161.9, 154.3, 132.0, 130.7, 127.7, 124.4, 115.2, 110.9, 108.9, 49.9, 45.9, 40.8, IR (ATR, cm -1 ) 3309, 2936, S20

21 1652, 1621, 1510, 1458, 1300, 1252, 1179, 1023, 925, 825, 719, 591. HRMS Calcd for C17H20N2O2S2 [M+H] ; found [(3E)-3-(hydroxyimino)-3-(4-methoxyphenyl)propyl]-1Hpyrrole-2-carbaldehyde (13c). To a solution of oxime mixture 17 (30.0 mg, mmol) in aqueous methanol (5 ml) was added HgCl2 (51.0 mg, mmol) and HgO (27.9 mg, mmol) were added. The mixture was stirred vigorously and heated at reflux temperature for 1 h. The solution was filtered and the solvent was evaporated. The residue was dissolved in CHCl3 and filtrated. The residue was purified by silica gel column chromatography eluting with n-hexane/etoac (10:1) to give white a solid (18.6 mg, 79%), mp C. 1 H NMR (400 MHz, CDCl3) δ 9.56 (s, 1H), (bs, 1H, C=NOH), (m, A-part of AAˊBBˊ system, 2H, arom.), 6.92 (d, J = 3.4 Hz, 2H), (m, B-part of AAˊBBˊ system, 2H, arom.), 6.16 (bt, J = 3.2 Hz, 1H), 4.61 (t, J = 7.2 Hz, 2H, CH2), 3.81 (s, 3H, OCH3), 3.25 (t, J = 7.2 Hz, 2H, CH2). 13 C NMR (101 MHz, CDCl3) δ 179.8, 161.0, 156.8, 132.3, 131.6, 128.1, 127.9, 125.5, 114.3, 110.2, 55.6, 46.1, IR (ATR, cm -1 ) 2923, 1632, 1603, 1513, 1404, 1369, 1325, 1250, 1178, 1030, 929, 831, 753, 595; HRMS Calcd for C15H16N2O3 [M+H] + : ; found: Geometry Optimized Structures 11g + AuCl3 11i + AuCl3 Figure 1. Geometry optimized structures of 11g + AuCl3 and 11i + AuCl3 complexes; NBO charges and distances (in Å) between Au and carbon atoms. S21

22 Cartesian Coordinates for the Optimized Structures Geometry optimizations and frequency calculations 5 of complexes 11g and 11i with AuCl3 were performed with using the B3LYP 36 (Becke-3-parameter-Lee-Yang-Parr) hybrid level within 6-31G(d,p) and LANL2DZ 7 (Au) basis set. Natural bond orbital (NBO) 8 analysis was performed at the same level of theory to obtain the charge distribution of the structures. Structure 11g + AuCl3 X Y Z C C C C C C C C H H H H N C H H C C H Au Cl Cl Cl H C H N O H S22

23 Structure 11i + AuCl3 X Y Z C C C C C C C C H H H H H C H H C C C C C C H C H C H H H H Au Cl Cl Cl C H N O H S23

24 References (1) (a) Alfonsi, M.; Dell Acqua, M.; Facoetti, D.; Arcadi, A.; Abbiati, G.; Rossi, E. Eur. J. Org. Chem. 2009, (b) Abbiati, G.; Casoni, A.; Canevari, V.; Nava, D.; Rossi, E. Org. Lett. 2006, 8, (2) Bashiardes, G.; Safir, I.; Barbot, F. Synlett 2007, 11, (3) Menges, N.; Sari, O.; Abdullayev, Y.; Erdem, S. S.; Balci, M. J. Org. Chem. 2013, 78, (4) Abbiati, G.; Arcadi, A.; Bellinazzi, A.; Beccalli, E.; Rossi, E.; Zanzola, S.; Organica, C.; Marchesini, A. J. Org. Chem. 2005, 70, (5) Gaussian 09, Revision D.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, M. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, (6) (a) Becke, A. D. J. Chem. Phys. 1993, 98, (b) Becke, A. D. J. Chem. Phys. 1993, 98, (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. (7) PHay P. J., Wadt W. R. J. Chem. Phys. 1985, 82, 299. (8) (a) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 889. (b) Foster, J. P.; Weinhold, F. J. Am. Chem. Soc. 1980, 102, S24

25 Figure 2: 1 H and 13 C NMR Spectra of (5a) in CDCl3 (400 MHz) S25

26 Figure 3: 1 H and 13 C NMR Spectra of (6a) in CDCl3 (400 MHz) S26

27 Figure 4: 1 H and 13 C NMR Spectra of (6b) in CDCl3 (400 MHz) S27

28 Figure 5: 1 H and 13 C NMR Spectra of (6c) in CDCl3 (400 MHz) S28

29 Figure 6: 1 H and 13 C NMR Spectra of (7a) in CDCl3 (400 MHz) S29

30 Figure 7: 1 H and 13 C NMR Spectra of (7b) in CDCl3 (400 MHz) S30

31 Figure 8: 1 H and 13 C NMR Spectra of (7c) in CDCl3 (400 MHz) S31

32 Figure 9: 1 H and 13 C NMR Spectra of (9a) in CDCl3 (400 MHz) S32

33 Figure 10: 1 H and 13 C NMR Spectra of (9b) in CDCl3 (400 MHz) S33

34 Figure 11: 1 H and 13 C NMR Spectra of (10a) in CDCl3 (400 MHz) S34

35 Figure 12: 1 H and 13 C NMR Spectra of (10b) in CDCl3 (400 MHz) S35

36 Figure 13: 1 H and 13 C NMR Spectra of (11a) in CDCl3 (400 MHz) S36

37 Figure 14: 1 H Spectrum of 11b and 13 C NMR Spectrum of a mixture of 6b and 11b in CDCl3 (400 MHz) S37

38 Figure 15: 1 H and 13 C NMR Spectra of (11c) in CDCl3 (400 MHz) S38

39 Figure 16: 1 H and 13 C NMR Spectra of (11d) in CDCl3 (400 MHz) S39

40 Figure 17: 1 H (in CDCl3) and 13 C NMR Spectra of (11e) in CD3COCD3 (400 MHz) S40

41 Figure 18: 1 H and 13 C NMR Spectra of (11f) in CDCl3 (400 MHz) S41

42 Figure 19: 1 H and 13 C NMR Spectra of (11g) in CDCl3 (400 MHz) S42

43 Figure 20: 1 H and 13 C NMR Spectra of (11h) in CDCl3 (400 MHz) S43

44 Figure 21: 1 H and 13 C NMR Spectra of (11i) in CDCl3 (400 MHz) S44

45 Figure 22: 1 H and 13 C NMR Spectra of (11j) in CDCl3 (400 MHz) S45

46 Figure 23: 1 H and 13 C NMR Spectra of (12a) in CDCl3 (400 MHz) S46

47 Figure 24: 1 H and 13 C NMR Spectra of (12b) in CDCl3 (400 MHz) S47

48 Figure 25: 1 H and 13 C NMR Spectra of (12c) in CDCl3 (400 MHz) S48

49 Figure 26: 1 H and 13 C NMR Spectra of (13a) in CDCl3 (400 MHz) S49

50 Figure 27: 1 H and 13 C NMR Spectra of (13b) in CDCl3 (400 MHz) S50

51 Figure 28: HMBC Spectrum of (13b) in CDCl 3 (400 MHz) S51

52 Figure 29: 1 H and 13 C NMR Spectra of (13c) in CDCl 3 (400 MHz) S52

53 Figure 30: 1 H and 13 C NMR Spectra of (13d) in CDCl 3 (400 MHz) S53

54 Figure 31: 1 H NMR Spectrum of (13e) in CDCl 3 (400 MHz) S54

55 Figure 32: 1 H and 13 C NMR Spectra of (13f) in CDCl 3 (400 MHz) S55

56 Figure 33: 1 H and 13 C NMR Spectra of (13g) in CDCl 3 (400 MHz) S56

57 Figure 34: 1 H and 13 C NMR Spectra of (14) in CDCl 3 (400 MHz) S57

58 Figure 35: 1 H and 13 C NMR Spectra of (15) in CDCl 3 (400 MHz) S58

59 Figure 36: 1 H and 13 C NMR Spectra of (16) in CDCl 3 (400 MHz) S59

60 Figure 37: 1 H and 13 C NMR Spectra of (17) in CDCl 3 (400 MHz) S60

61 Figure 38: 1 H and 13 C NMR Spectra of (13c) in CDCl 3 (400 MHz) S61