Copper Catalyzed Formal Carbene Migratory Insertion into. Internal Olefinic C=C Bonds with N-Tosylhydrazones to Access

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1 Supporting Information for Copper Catalyzed Formal Carbene Migratory Insertion into Internal Olefinic C=C Bonds with N-Tosylhydrazones to Access Iminofuran and 2(3H)-furanone Derivatives Fei Huang,,, Zhuqing Liu,,, Quannan Wang,, Jiang Lou, and Zhengkun Yu*,, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 6023, P. R. China University of Chinese Academy of Sciences, Beijing 00049, P. R. China State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai , P. R. China These authors contributed equally to this work. Experimental procedures and analytical data Contents: page. General considerations S2 2. Experimental procedures S3 3. X-Ray crystallographic studies S0 4. Analytical data for known compounds S2 5. Analytical data for new compounds S6 6. Copies of NMR spectra S49 S

2 . General considerations The solvents were dried and distilled prior to use by the literature methods. H and 3 C{ H} NMR spectra were recorded on a 400 MHz spectrometer and all chemical shift values refer to CDCl 3 ( ( H), 7.26 ppm; ( 3 C), 77.6 ppm). X-ray Crystallographic analysis was achieved by the Analysis Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. The HRMS analysis was obtained on a Waters GC-TOF mass spectrometer. All the chemical reagents were purchased from commercial sources and used as received unless otherwise indicated. Compounds a, j-k, b and c, 2 m, 3 o, 3 q, 3 2a-2p, 4 2q, 5 5b, 6 (E)-3-(benzylamino)-3-methoxy--phenylprop-2-en--one (9a), 7 (E)-3-(benzylamino) -3-ethoxy--phenylprop-2-en--one (9b), 8 and 3,3-bis- (benzylamino)--phenylprop- 2-en--one (0) 9 were prepared as reported. Compound 7a 0 was known and its spectroscopic feature is in good agreement with that reported in the literatures. References () Singh, S. J.; Singh, O. M. Tetrahedron Lett. 2008, 49, 399. (2) Yang, C.-W.; Bai, Y.-X.; Zhang, N.-T.; Zeng, C.-C.; Hu, L.-M.; Tian, H.-Y. Tetrahedron 202, 68, 020. (3) Zhang, T.; Jia, Y.-M.; Yan, S.-J.; Yu, C.-Y.; Huang, Z.-T. Arkivoc 2009, 4, 56. (4) Fulton, J.; Aggarwal, V.; de Vicente, J. Eur. J. Org. Chem. 2005, 8, 479. (5) Feng, X. W.; Wang, J.; Zhang, J.; Yang, J.; Wang, N.; Yu, X. Q. Org. Lett. 200, 2, (6) Lee, D. J.; Kim, K. J. Org. Chem. 2004, 69, (7) (a) Kawade, R. K.; Tseng, C.-C.; Liu, R.-S. Chem. - Eur. J. 204, 20, 3927; (b) Barun, O.; Ila, H.; Junjappa, H. J. Org. Chem. 2000, 65, 583. (8) Braibante, M. E. F.; Braibante, H. T. S.; Roza, J. K. D.; Henriques, D. M.; Tavares, L. D. C. Synthesis 2003, 8, 60. (9) Alonso-Alija, C.; Michels, M.; Schirok, H.; Schlemmer, K.-H.; Bell, J.; Fitzgerald, M. F.; Dodd, S.; Gill, A. A. PCT Int. Appl. 2003, (0) Endo, K.; Yakeishi, S.; Takayama, R.; Shibata, T. Chem. - Eur. J. 204, 20, S2

3 2. Experimental procedures 2. Screening of conditions for the reactions of a with 2a Table S. Screening of reaction conditions. a Entry a:2a:base Catalyst Base Solvent Yield b (%) :.5:2.5 CuI K 2 CO 3 toluene 35 2 :.5:2.5 CuI tbuona toluene < 3 :.5:2.5 CuI tbuoli toluene 44 4 :.5: CuI tbuoli toluene 38 5 :2:2 CuI tbuoli toluene 65 6 :3:3 CuI tbuoli toluene 72 7 c :3:3 CuI tbuoli toluene 42 8 :3:3 CuI tbuoli,4-dioxane (53) 9 :3:3 CuI tbuoli DCE (32) 0 :3:3 CuCl tbuoli toluene (20) :3:3 CuBr tbuoli toluene (38) 2 :3:3 CuOAc tbuoli toluene 0 3 :3:3 CuBr 2 tbuoli toluene 75 4 d :3:3 CuBr 2 tbuoli toluene 72 a Conditions: a (0.3 mmol), 2a ( equiv), catalyst (0.06 mmol), base ( equiv), solvent (3 ml), 0 o C, 0. MPa N 2, 2 h. b Isolated yield. The yield determined by proton NMR measurement with,3,5-trimethoxybenzene as the internal standard is given in the parentheses. c 90 o C. d Using 5 mol % CuBr 2 catalyst. 2.2 Preparation of α-oxo ketene N,S-acetals () A typical procedure for the synthesis of α-oxo ketene N,S-acetals (a-t) Synthesis of a: A mixture of ketene S,S-acetal sma (448 mg, 2 mmol) and benzylamine (437 μl, 4 mmol) in EtOH (5 ml) was stirred at 80 o C overnight. After acetal sma was completely consumed by TLC monitoring on silica gel, the resultant mixture was cooled to ambient temperature and evaporated all the volatiles under reduced pressure. The residue was purified by silica gel column chromatography S3

4 (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording a (489 mg, 86%) as a yellow solid. Synthesis of (E)-3-(diethylamino)-3-(thiomethyl)--p-tolylprop-2-en--one (u): In a fashion similar to the synthesis of a, ketene S,S-acetal smb (476 mg, 2 mmol) reacted with diethylamine (292 ul, 4 mmol) in CH 3 CN at 80 o C to afford u (280 mg, 53%) as a yellow liquid Preparation of N-tosylhydrazones (2) A typical procedure for the synthesis of N-tosylhydrazones (2a-p) Synthesis of 2a: To a stirred solution of p-toluenesulfonyl hydrazide (.86 g, 0 mmol) in methanol (50 ml) at 65 o C was dropwise added acetophenone (.5 ml, 0 mmol) within 20 minutes, and stirring was continued for 2 h. The resultant mixture was then cooled to 0 C to give a crystalline precipitate which was collected by filtration, washed with 5 ml petroleum ether (60-90 o C), and dried in vacuo. Compound 2a was thus obtained as a white solid (2.6 g, 90%). Synthesis of N'-(di-p-tolylmethylene)-4-methylbenzenesulfonohydrazide 2q: In a fashion similar to the synthesis of 2a, the reaction of p-toluenesulfonyl hydrazide (.86 g, 0 mmol) and 4,4 -dimethylbenzophenone (2. g, 0 mmol) in the presence of concentrated hydrochloric acid (0.5 ml) afforded 2q as a white solid (2.73 g, 72%) Preparation of α-thioxo ketene N,S-acetals (5) S4

5 A typical procedure for the synthesis of α-thioxo ketene N,S-acetals (5) Synthesis of 5a: A mixture of α-oxo ketene N,S-acetal a (.42 g, 5.0 mmol) and Lawesson s reagent (.00 g, 2.5 mmol) in toluene (0 ml) was stirred at 20 o C overnight. After a was completely consumed by TLC monitoring on silica gel, the reaction mixture was cooled to ambient temperature and evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 5a as a red solid (.7 g, 78%) Preparation of α-oxo ketene N,O-acetals (9) and N,N-acetal (0) A typical procedure for the synthesis of α-oxo ketene N,O-acetals (9) Synthesis of (E)-3-(benzylamino)-3-methoxy--phenylprop-2-en--one (9a): A mixture of NaOMe (270 mg, 5 mmol) and N,S-acetal a (.42 g, 5 mmol) in MeOH (20 ml) was stirred at 65 o C for 2 h until a was completely consumed by TLC monitoring on silica gel. The reaction mixture was then cooled to ambient temperature, quenched with 50 ml saturated aqueous NH 4 Cl and extracted with dichloromethane (3 0 ml). The combined extracts were washed with 0 ml water, dried over anhydrous Na 2 SO 4, filtered, and evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 9a as a white solid (.08 g, 75%). A typical procedure for the synthesis of 3,3-bis(benzylamino)-- phenylprop-2-en--one (0): A mixture of ketene S,S-acetal sma (448 mg, 2 mmol) S5

6 and benzylamine (874 ul, 8 mmol) in EtOH (5 ml) was stirred at 00 o C for 6 days. The mixture was then cooled to ambient temperature and evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 0 as a yellow solid (287 mg, 42%). 2.6 Typical procedures for the synthesis of iminofurans (3), γ-ketoamides (4), and iminothiophenes (6) A typical procedure for the synthesis of iminofurans (3) Synthesis of 3a: Under a nitrogen atmosphere, a mixture of N,S-acetal a (42 mg, 0.5 mmol), N-tosylhydrazone 2a (432 mg,.5 mmol), CuBr 2 (22 mg, 0. mmol), and tbuoli (20 mg,.5 mmol) in 5 ml toluene was stirred at 0 C for 24 h. The reaction mixture was cooled to ambient temperature, filtered through a short pad of celite, rinsed with 20 ml of ethyl acetate, and evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 3a as a colourless liquid (28.0 mg, 75%). A typical procedure for the synthesis of γ-ketoamides (4) Synthesis of 4a: Under a nitrogen atmosphere, a mixture of N,S-acetal u (32 mg, 0.5 mmol), N-tosylhydrazone 2a (432 mg,.5 mmol), CuBr 2 (22 mg, 0. mmol), tbuoli (20 mg,.5 mmol) and H 2 O (8 ul, mmol) in 5 ml toluene was stirred at 0 C for 24 h. The reaction mixture was then cooled to ambient temperature, filtered through a short pad of celite, rinsed with 20 ml of ethyl acetate, and evaporated all the volatiles under S6

7 reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 4a as a yellow solid (68 mg, 40%). A typical procedure for the synthesis of iminothiophenes (6) Synthesis of 6a: Under a nitrogen atmosphere, a mixture of N,S-acetal 5a (50 mg, 0.5 mmol), N-tosylhydrazone 2a (432 mg,.5 mmol), CuBr 2 (22 mg, 0. mmol), and tbuoli (20 mg,.5 mmol) in 5 ml toluene was stirred at 0 C for h. The reaction mixture was cooled to ambient temperature, filtered through a short pad of celite, rinsed with 20 ml of ethyl acetate, and evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 6a as a yellow liquid (9 mg, 67%). 2.7 Scale-up preparation of iminofuran 3r Synthesis of (E)--(furan-2-yl)-N-(3-methyl-3,5-diphenylfuran-2(3H)-ylidene) methanamine (3r): Under a nitrogen atmosphere, a mixture of ketene N,S-acetal r (.37 g, 5 mmol), N-tosylhydrazone 2a (2.88 g, 0 mmol), CuBr 2 (223 mg, mmol), and tbuoli (800 mg, 0 mmol) in 20 ml toluene was stirred at 0 C for 8 h. The reaction mixture was then cooled to ambient temperature, filtered through a short pad of celite, rinsed with 50 ml of ethyl acetate, and evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 3r as a white solid (.7 g, 7%). S7

8 2.8 Hydrolysis of iminofurans 3 Synthesis of 2(3H)-furanone 7a: A mixture of iminofuran 3r (66 mg, 0.2 mmol), 0% aqueous H 2 SO 4 (0.2 ml), and ethanol (2 ml) was stirred at reflux for 5 min, cooled to ambient temperature, and then evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 7a as a colorless liquid (46 mg, 9%). Synthesis of 4-oxo-butanoate ( -ketoester) 8a: In a fashion similar to the synthesis of 7a, the hydrolysis reaction of 3r (66 mg, 0.2 mmol) was conducted under the same conditions for 2 h, affording 8a as a colorless liquid (5 mg, 86%). 2.9 Control experiments Radical trapping reactions: Under a nitrogen atmosphere, a mixture of N,S-acetal a (42 mg, 0.5 mmol), N-tosylhydrazone 2a (432 mg,.5 mmol), TEMPO (78 mg, 0.5 mmol), CuBr 2 (22 mg, 0. mmol), and tbuoli (20 mg,.5 mmol) in 5 ml toluene was stirred at 0 C for 24 h. The reaction mixture was cooled to ambient temperature, filtered through a short pad of celite, rinsed with 20 ml of ethyl acetate, and evaporated all the volatiles under reduced pressure. The S8

9 resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 3a as a colorless liquid ( mg, 65%). Under a nitrogen atmosphere, a mixture of N,S-acetal a (42 mg, 0.5 mmol), N-tosylhydrazone 2a (432 mg,.5 mmol), BHT (0 mg, 0.5 mmol), CuBr 2 (22 mg, 0. mmol), and tbuoli (20 mg,.5 mmol) in 5 ml toluene was stirred at 0 C for 24 h. The reaction mixture was cooled to ambient temperature, filtered through a short pad of celite, rinsed with 20 ml of ethyl acetate, and evaporated all the volatiles under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C)/AcOEt = 30:, v/v), affording 3a as a colorless liquid (20 mg, 7%). One-pot, two-step reaction of a and 2a: Under a nitrogen atmosphere, a mixture of N-tosylhydrazone 2a (432 mg,.5 mmol) and tbuoli (20 mg,.5 mmol) in 5 ml toluene was stirred at 0 C for 45 min. Then N,S-acetal a (42 mg, 0.5 mmol) and CuBr 2 (22 mg, 0. mmol) were added to the resultant mixture, and stirring was continued at 0 o C for 2 h. The reaction mixture was cooled to ambient temperature, filtered through a short pad of celite, rinsed with 20 ml of ethyl acetate, and evaporated all the volatiles under reduced pressure. The residue was purified by silica gel column chromatography (eluent: petroleum ether (60-90 C) /AcOEt = 30:, v/v), affording 3a as a colorless liquid (8 mg, 70%). Reactions of ketene acetals (9 and 0) and enamine 0 with 2a: Under a nitrogen atmosphere, a mixture of N,O-acetal 9a (or 9b, 0, and ) (0.5 mmol), S9

10 N-tosylhydrazone 2a (432 mg,.5 mmol), CuBr 2 (22 mg, 0. mmol), and tbuoli (20 mg,.5 mmol) in 5 ml toluene was stirred at 0 C for 24 h. The resultant mixture was cooled to ambient temperature and subject to proton NMR analysis in CDCl 3. The target product 3a was not detected in the reaction mixtures. 3. X-Ray crystallographic studies Single crystals of compounds 3z5 and 4a were grown in petroleum ether (60-90 C)/CH 2 Cl 2 (v/v, 3/) at -20 C and their X ray diffraction studies were carried out on a SMART APEX diffractometer with graphite-monochromated Mo radiation (λ = Å). Cell parameters were obtained by global refinement of the positions of all collected reflections. Intensities were corrected for Lorentz and polarization effects and empirical absorption. The structures were solved by direct methods and refined by full-matrix least squares on F 2. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed in calculated positions. Structure solution and refinement were performed by using the SHELXL-97 package. The X-ray crystallographic files, in CIF format, are available from the Cambridge Crystallographic Data Centre on quoting the deposition numbers CCDC for 3z5 and CCDC for 4a. Copies of this information may be obtained free of charge from The Director, CCDC, 2 Union Road, Cambridge CB2 IEZ, UK (Fax: ; deposit@ccdc.cam.ac.uk or www: ccdc.cam.ac.uk). Figure S. Molecular structure of compound 3z5. S0

11 Table S2. Crystal data and structure refinement for 3z5. Empirical formula C 25 H 23 NO 2 Formula weight Temperature 293(2) K Wavelength Å Crystal system, space group Orthorhombic Unit cell dimensions a = (7) Å = 90 b = 9.232(6) Å = 90 c = (2) Å = 90 Volume 998.8(3) Å 3 Z, Calculated density 4,.228 Mg/m 3 Absorption coefficient mm - F(000) 784 Crystal size x 0.70 x 0.30 mm 3 Theta range for data collection to Index ranges -<=h<=0, -9<=k<=, -29<=l<=20 Reflections collected/unique 7466 Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission.0000 and Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 3762 / 0 / 256 Goodness-of-fit on F Final R indices [I > 2 sigma(i)] R = , wr2 = R indices (all data) R = , wr2 = Largest diff. peak and hole 0.5 and e.å -3 Figure S2. Molecular structure of compound 4a. S

12 Table S3. Crystal data and structure refinement for 4a. Empirical formula C 22 H 27 NO 2 Formula weight Temperature 293(2) K Wavelength Å Crystal system, space group Monoclinic a = (5) Å = 90 Unit cell dimensions b = 6.735(6) Å = 96.37(7) c = 8.60(9) Å = 90 Volume 969.7(3) Å 3 Z, Calculated density 4,.38 Mg/m 3 Absorption coefficient mm - F(000) 728 Crystal size 0.90 x 0.50 x 0.0 mm 3 Theta range for data collection to Index ranges -6<=h<=7, -3<=k<=9, -8<=l<=22 Reflections collected/unique 85 Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission.0000 and Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 347 / 36 / 249 Goodness-of-fit on F 2.0 Final R indices [I > 2 sigma(i)] R = , wr2 = R indices (all data) R = , wr2 = Largest diff. peak and hole and e.å Analytical data for known compounds (E)-3-(Benzylamino)-3-(thiomethyl)--phenylprop-2-en--one (a): 2.29 g, yield 8%, white solid. H NMR (400 MHz, CDCl 3 ) δ 2.2 (s, H, NH), 7.88, 7.43, 7.36, and 7.30 (m each, 2:3:4: H, aromatic CH), 5.73 (s, H, CH=C-S), 4.62 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.47 (d, J = 0.9 Hz, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.7 (Cq, C=O), 69.6 (Cq, CSMe), 40.7 and 37.3 (Cq each, i-c of Ph), 30.7, 28.9, 28.3, 27.8, 27.4, and 27. (aromatic CH), 87.0 (CH=C-S), 48.0 (NH-CH 2 ), 4.6 (SCH 3 ). S2

13 (E)-3-(Benzylamino)-3-(thiomethyl)--p-tolylprop-2-en--one (b): 2.20 g, yield 74%, white solid. H NMR (400 MHz, CDCl 3 ) δ 2.6 (s, H, NH), 7.77 and 7.2 (d each, J = 8. Hz, 2:2 H, aromatic CH), 7.35 and 7.29 (m each, 4: H, aromatic CH), 5.72 (s, H, CH=C-S), 4.6 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.47 (s, 3 H, C 6 H 4 -CH 3 ), 2.39 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.6 (Cq, C=O), 69.2 (Cq, CSMe), 4.0, 38.0, and 37.4 (Cq each), 29.0, 28.9, 27.7, 27.5, and 27. (aromatic CH), 86.9 (CH=C-S), 48.0 (NH-CH 2 ), 2.5 (C 6 H 4 -CH 3 ), 4.6 (SCH 3 ). (E)-3-(Benzylamino)--(4-chlorophenyl)-3-(thiomethyl)prop-2-en--one (c): 2.4 g, yield 76%, white solid. H NMR (400 MHz, CDCl 3 ) δ 2.8 (s, H, NH), 7.80, 7.36, and 7.30 (m each, 2:6: H, aromatic CH), 5.66 (s, H, CH=C-S), 4.6 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.47 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 84. (Cq, C=O), 70.0 (Cq, CSMe), 39., 37., and 36.7 (Cq each), 28.9, 28.5, 28.4, 27.8, and 27.4 (aromatic CH), 86.6(CH=C-S), 48.0 (NH-CH 2 ), 4.5 (SCH 3 ). (E)-3-(Methylamino)-3-(thiomethyl)--phenylprop-2-en--one (j):.70 g, yield 8%, white solid. H NMR (400 MHz, CDCl 3 ) δ.73 (s, H, NH), 7.82 and 7.35 (m each, 2:3 H, aromatic CH), 5.6 (d, J =.6 Hz, H, CH=C-S), 2.98 (m, 3 H, NH-CH 3 ), 2.37 (m, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 84.9 (Cq, C=O), 70.5 (Cq, CSMe), 40.6 (Cq, i-c of Ph), 30.2, 28.0, and 26.7 (aromatic CH), 86. (CH=C-S), 30.0 (NH-CH 3 ), 4.0 (SCH 3 ). (E)-3-(Ethylamino)-3-(thiomethyl)--phenylprop-2-en--one (k):.8 g, yield 82%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ.69 (s, H, NH), 7.74 and 7.26 (m each, 2:3 H, aromatic CH), 5.52 (s, H, CH=C-S), 3.28 (m, 2 H, NH-CH 2 ), S3

14 2.29 (s, 3 H, SCH 3 ),.9 (t, J = 7.2 Hz, 3 H, CH 2 -CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 84.9 (Cq, C=O), 69.3 (Cq, CSMe), 40.6 (Cq, i-c of Ph), 30.2, 28., and 26.7 (aromatic CH), 85.9 (CH=C-S), 38.6 (NH-CH 2 ), 4.7 (SCH 3 ), 4.0 (CH 2 -CH 3 ). (E)-3-(Allylamino)-3-(thiomethyl)--phenylprop-2-en--one (m): 2.29 g, yield 85%, white liquid. H NMR (400 MHz, CDCl 3 ) δ.9 (s, H, NH), 7.85 and 7.40 (m each, 2:3 H, aromatic CH), 5.90 (m, H, CH=CH 2 ), 5.68 (s, H, CH=C-S), 5.32 (dd, J = 7.,. Hz, H, CH=CH 2 ), 5.2 (dd, J = 0.3,. Hz, H, CH=CH 2 ), 4.0 (m, 2 H, NH-CH 2 ), 2.43 (dd, J = 7., 2.5 Hz, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.4 (Cq, C=O), 69.5 (Cq, CSMe), 40.7 (Cq, i-c of Ph), 32.9 and 7. (CH=CH 2 ), 30.5, 28.2, and 26.9 (aromatic CH), 86.8 (CH=C-S), 46.2 (NH-CH 2 ), 4.4 (SCH 3 ). (E)-3-(Butylamino)-3-(thiomethyl)--phenylprop-2-en--one (o): 2.09 g, yield 84%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ.87 (s, H, NH), 7.83 and 7.36 (m each, 2:3 H, aromatic CH), 5.6 (s, H, CH=C-S), 3.34 (q, J = 6.5 Hz, 2 H, NH-CH 2 ), 2.39 (s, 3 H, SCH 3 ),.64 (m, 2 H, NH-CH 2 -CH 2 -CH 2 ),.43 (m, 2 H, NH-CH 2 -CH 2 -CH 2 ), 0.93 (t, J = 7.3 Hz, 3 H, CH 2 -CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 84.9 (Cq, C=O), 69.5 (Cq, CSMe), 40.7 (Cq, i-c of Ph), 30.3, 28., and 26.8 (aromatic CH), 85.9 (CH=C-S), 43.6 (NH-CH 2 ), 3.5 and 20.0 (CH 2 ), 4. (SCH 3 ), 3.6 (CH 2 -CH 3 ). (E)-3-(Cyclohexylamino)-3-(thiomethyl)--phenylprop-2-en--one (q): 2.2 g, yield 77%, colorless solid. H NMR (400 MHz, CDCl 3 ) δ.97 (d, J = 7.3 Hz, H, NH), 7.84 and 7.38 (m each, 2:3 H, aromatic CH), 5.6 (s, H, CH=C-S), 3.6 (m, H, NH-CH), 2.44 (s, 3 H, SCH 3 ),.97,.78,.58,.43, and.30 (m, 2:2::3:2 H, cyclohexyl CH). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.0 (Cq, C=O), 68. (Cq, S4

15 CSMe), 40.9 (Cq, i-c of Ph), 30.4, 28.2, and 26.9 (aromatic CH), 86.0 (CH=C-S), 52.9 (NH-CH), 33.2, 25.4, and 24.4 (cyclohexyl CH), 4.3 (SCH 3 ). (E)-3-(Ethylamino)-3-(thiomethyl)--phenylprop-2-ene--thione (5b): 2.29 g, yield 84%, red solid. H NMR (400 MHz, CDCl 3 ) δ 4.49 (s, H, NH), 7.68 and 7.34 (m each, 2:3 H, aromatic CH), 6.5 (s, H, CH=C-S), 3.54 (m, 2 H, NH-CH 2 ), 2.49 (s, 3 H, SCH 3 ),.43 (t, J = 7.3 Hz, 3 H, CH 2 CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 96.6 (Cq, C=S), 7.3 (Cq, CSMe), 49.3 (Cq, i-c of Ph), 29.0, 28., and 26.9 (aromatic CH), 06.8 (CH=C-S), 39.6 (NH-CH 2 ), 4.5 (CH 3 ), 4. (CH 3 ). 3-Methyl-3,5-diphenylfuran-2(3H)-one (7a): 46 mg, yield 9%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.70 (dd, J = 7.9,.5 Hz, 2H, aromatic CH), 7.43 (m, 8H, aromatic CH), 6.4 (s, H, furyl CH),.83 (s, 3H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 79.5 (Cq, C=O), 5.8, 39.7 and 28.3 (Cq each), 29.9, 29.0, 28.9, 27.9, 26.2 and 25. (aromatic CH), 08.6 (furyl CH), 52.6 (Cq, C-CH 3 ), 25. (CH 3 ). (E)-3-(Benzylamino)-3-methoxy--phenylprop-2-en--one (9a):.08 g, yield 75%, white solid. H NMR (400 MHz, CDCl 3 ) δ.35 (s, H, NH), 7.87 (dd, J = 7.5, 2.0 Hz, 2 H, aromatic CH), 7.42 (d, J = 7. Hz, 3 H, aromatic CH), 7.34 and 7.28 (m each, 4: H, aromatic CH), 5.47 (s, H, CH=C-O), 4.54 (d, J = 6. Hz, 2 H, NH-CH 2 ), 3.89 (s, 3 H, OCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 87. (Cq, C=O), 69.3 (Cq, CONH), 40.9 and 38.2 (Cq each), 30.5, 28.8, 28.3, 27.4, 27.3, and 26.8 (aromatic CH), 73.6 (CH=C-O), 55.8 (OCH 3 ), 44. (NH-CH 2 ). (E)-3-(Benzylamino)-3-ethoxy--phenylprop-2-en--one (9b):.9 g, yield 85%, white solid. H NMR (400 MHz, CDCl 3 ) δ.4 (s, H, NH), 7.86, 7.40, 7.34, S5

16 and 7.28 (m each, 2:3:4: H, aromatic CH), 5.44 (s, H, CH=C-O), 4.54 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 4.6 (q) and.39 (t) (J = 7.0 Hz, 2:3 H, OCH 2 CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 86.9 (Cq, C=O), 68.6 (Cq, CONH), 4.0 and 38.3 (Cq each), 30.4, 28.7, 28.2, 27.5, 27.4, and 26.8 (aromatic CH), 74.3 (CH=C-O), 64.6 (OCH 2 CH 3 ), 44.2 (NH-CH 2 ), 4.5 (OCH 2 CH 3 ). 3,3-Bis(benzylamino)--phenylprop-2-en--one (0): 0.72 g, yield 42%, white solid. H NMR (400 MHz, CDCl 3 ) δ.88 (s, H, NH), 7.79 (d, J = 7.2 Hz, 2H), 7.36 and 7.29 (m each, 7:4 H, aromatic CH), 7. (d, J = 6.4 Hz, 2 H, aromatic CH), 5.32 (s, H, CH=C), 4.68 (s, H, NH), 4.45 (d, J = 5.5 Hz, 2 H, NH-CH 2 ), 4.32 (d, J = 5.0 Hz, 2 H, NH-CH 2 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 84.9 (Cq, C=O), 6.9 (Cq, CNBn), 4.9, 37.3, and 37.0 (Cq each), 29.7, 29., 28.9, 28., 27.8, 27.8, 27., 27.0, and 26.6 (aromatic CH), 76.0 (CH=C), 46.5 (NH-CH 2 ), 44.8 (NH-CH 2 ). 5. Analytical data for new compounds (E)-3-(Benzylamino)-3-(thiomethyl)--(4-(trifluoromethyl)phenyl)prop-2-en- -one (d): 2.35 g, yield 67%, yellow solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 2.30 (s, H, NH), 7.97 and 7.66 (d each, J = 8. Hz, 2:2 H, aromatic CH), 7.38 and 7.32 (m each, 4: H, aromatic CH), 5.7 (s, H, CH=C-S), 4.6 (d, J = 5.9 Hz, 2 H, NH-CH 2 ), 2.45 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 83.6 (Cq, C=O), 70.6 (Cq, CSMe), 43.9, and 36.8 (Cq each), 32.0 (q, J = 32.3 Hz, Cq, C-CF 3 ), 28.9, 27.8, 27.4, 27.3, and 25.3 (q, J = 3.7 Hz) (aromatic CH), 24. (q, J = Hz, Cq, CF 3 ), 86.9 (CH=C-S), 48.0 (NH-CH 2 ), 4.4 (SCH 3 ). HRMS (EI) calcd for C 8 H 7 NOSF 3 [M+H] + : ; Found: S6

17 (E)-3-(Benzylamino)--(3-fluorophenyl)-3-(thiomethyl)prop-2-en--one (e): 2.50 g, yield 83%, yellow solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 2.2 (s, H, NH), 7.64 (d, J = 7.8 Hz, H, aromatic CH), 7.57, 7.36, 7.30, and 7.2 (m each, :5:: H, aromatic CH), 5.67 (s, H, CH=C-S), 4.6 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.46 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 83.8 (Cq, C=O), 70.2 (Cq, CSMe), 62.9 (d and Cq, J = Hz, aromatic C-F), 43. (d and Cq, J = 6.2 Hz, i-c of C 6 H 4 ), 37.0 (Cq, aromatic C-CH 2 ), 29.8 (d, J = 7.8 Hz, aromatic CH), 28.9, 27.8, and 27.4 (aromatic CH), 22.6 (d, J = 2.8 Hz, aromatic CH), 7.4 (d, J = 2.4 Hz, aromatic CH), 3.9 (d, J = 22.2 Hz, aromatic CH), 86.7 (CH=C-S), 48.0 (NH-CH 2 ), 4.5 (SCH 3 ). HRMS (EI) calcd for C 7 H 7 NOSF [M+H] + : ; Found: (E)-3-(Benzylamino)--(2-chlorophenyl)-3-(thiomethyl)prop-2-en--one (f): 2.4 g, yield 76%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ.96 (s, H, NH), 7.5, 7.38, 7.32, and 7.28 (m each, :5::2 H, aromatic CH), 5.4 (s, H, CH=C-S), 4.63 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.4 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 86. (Cq, C=O), 69.9 (Cq, CSMe), 4.6 (Cq, i-c of C 6 H 4 ), 37.0 (Cq, aromatic C-CH 2 ), 30.9 (Cq, aromatic C-Cl), 30.2, 30.0, 29.5, 28.9, 27.8, 27.5, and 26.7 (aromatic CH), 9.2(CH=C-S), 48. (NH-CH 2 ), 4.5 (SCH 3 ). HRMS (EI) calcd for C 7 H 7 NOSCl [M+H] + : ; Found: (E)-3-(Benzylamino)-3-(thiomethyl)--(naphthalen-2-yl)prop-2-en--one (g): 2.80 g, yield 84%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 2.33 (s, H, NH), 8.4 (s, H, aromatic CH), 8.00 (dd, J = 8.6,.7 Hz, H, aromatic CH), 7.95 (dd, J = 6.0, 3.3 Hz, H, aromatic CH), 7.87 (dd, J = 8.8, 6.4 Hz, 2 H, aromatic CH), 7.52, 7.38, and 7.32 (m each, 2:4: H, aromatic CH), 5.89 (s, H, CH=C-S), 4.64 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.50 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, S7

18 CDCl 3 ) δ 85.3 (Cq, C=O), 69.6 (Cq, CSMe), 38.0, 37.2, 34.6, and 33.0 (Cq each), 29.2, 28.9, 28.0, 27.7, 27.6, 27.4, 27.2, 27., 26.3, and 24.2 (aromatic CH), 87.2 (CH=C-S), 48.0 (NH-CH 2 ), 4.5 (SCH 3 ). HRMS (EI) calcd for C 2 H 20 NOS [M+H] + : ; Found: (E)-3-(Benzylamino)--(furan-2-yl)-3-(thiomethyl)prop-2-en--one (h): 2.29 g, yield 84%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ.9 (s, H, NH), 7.46 (s, H, furyl CH), 7.34 and 7.28 (m each, 4: H, aromatic CH), 7.0 (d, J = 3.4 Hz, H, furyl CH), 6.47 (dd, J = 3.3,.7 Hz, H, furyl CH), 5.7 (s, H, CH=C-S), 4.59 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.47 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 75.0 (Cq, C=O), 69.9 (Cq, CSMe), 54.4, and 37. (Cq each), 43.9, 2.5, and 2.0 (furyl CH), 28.9, 27.7, and 27.4 (aromatic CH), 86.2 (CH=C-S), 48.0 (NH-CH 2 ), 4.5 (SCH 3 ). HRMS (EI) calcd for C 5 H 6 NO 2 S [M+H] + : ; Found: (E)-3-(Benzylamino)-3-(thiomethyl)--(thiophen-2-yl)prop-2-en--one (i): 2.3 g, yield 80%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ.79 (s, H, NH), 7.55 (dd, J = 3.7,. Hz, H, thienylch), 7.43 (dd, J = 5.0,. Hz, H, thienylch) and 7.06 (dd, J = 4.9, 3.7 Hz, H, thienylch), 7.35 and 7.29 (m, 4: H, aromatic CH), 5.62 (s, H, CH=C-S), 4.58 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 2.45 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 78.6 (Cq, C=O), 69.2 (Cq, CSMe), 47. (Cq, thienylc-co), 37. (Cq, aromatic C-CH 2 ), 29.8, 28.8, 27.7, 27.4, and 27.3 (aromatic CH and thienylch), 86.5 (CH=C-S), 48.0 (NH-CH 2 ), 4.5 (SCH 3 ). HRMS (EI) calcd for C 5 H 6 NOS 2 [M+H] + : ; Found: S8

19 (E)-3-(Ethylamino)--(3-methoxyphenyl)-3-(thiomethyl)prop-2-en--one (l): 2.03 g, yield 8%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ.65 (s, H, NH), 7.29 (d, J = 2. Hz, H, aromatic CH), 7.25 (d) and 7.0 (t) (J = 7.8 Hz, : H, aromatic CH), 6.78 (dd, J = 8., 2.3 Hz, H, aromatic CH), 5.45 (s, H, CH=C-S), 3.6 (s, 3 H, OCH 3 ), 3.9 (m, 2 H, NH-CH 2 ), 2.20 (s, 3 H, SCH 3 ),. (t, J = 7.2 Hz, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 83.8 (Cq, C=O), 69.0 (Cq, CSMe), 59. and 4.7 (Cq each), 28.6, 8.6, 5.8, and.4 (aromatic CH), 85.5 (CH=C-S), 54.6 (OCH 3 ), 38.2 (NH-CH 2 ), 4.3 (CH 3 ), 3.5 (CH 3 ). HRMS (EI) calcd for C 3 H 8 NO 2 S [M+H] + : ; Found: (E)-3-(Allylamino)--(4-chlorophenyl)-3-(thiomethyl)prop-2-en--one (n): 2.22 g, yield 83%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ.86 (s, H, NH), 7.73 and 7.29 (m each, 2:2 H, aromatic CH), 5.84 (m, H, CH=CH 2 ), 5.56 (s, H, CH=C-S), 5.27 and 5.7 (m each, : H, CH=CH 2 ), 3.94 (m, 2 H, NH-CH 2 ), 2.36 (m, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 83.5 (Cq, C=O), 69.8 (Cq, CSMe), 38.8 and 36.3 (Cq each), 32.6 and 7.0 (CH=CH 2 ), 28.2 and 28. (aromatic CH), 86.3 (CH=C-S), 46. (NH-CH 2 ), 4.2 (SCH 3 ). HRMS (EI) calcd for C 3 H 5 NOSCl [M+H] + : ; Found: (E)-3-(Thiomethyl)-3-(octadecylamino)--phenylprop-2-en--one (p): 0.85 g, yield 95%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ.86 (s, H, NH), 7.84 and 7.40 (m each, 2:3 H, aromatic CH), 5.64 (s, H, CH=C-S), 3.37 (dd, J = 2.8, 6.9 Hz, 2 H, NH-CH 2 ), 2.46 (s, 3 H, SCH 3 ),.65 (m, 2 H, NH-CH 2 -CH 2 ),.42 (m, 2 H, NH-CH 2 - CH 2 -CH 2 ),.26 (s, 28 H, 4 CH 2 ), 0.88 (t, J = 6.8 Hz, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.2 (Cq, C=O), 69.6 (Cq, CSMe), 4.0 (Cq, i-c of Ph), 30.5, 28.3, and 27.0 (aromatic CH), 86.2 (CH=C-S), 44.2 (NH-CH 2 ), 32., 29.8, 29.78, 29.77, 29.72, 29.70, 29.6, 29.5, 29.4, 27.0, 22.8, and 4.2 (CH 2 ), 4.4 (SCH 3 ). HRMS (EI) calcd for C 28 H 48 NOS [M+H] + : ; Found: S9

20 (E)-3-(Furan-2-ylmethylamino)-3-(thiomethyl)--phenylprop-2-en--one (r): 2.29 g, yield 84%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 2.04 (s, H, NH), 7.85 (dd, J = 7.9,.7 Hz, 2 H, aromatic CH), 7.4 (m, 3 H of aromatic CH and H of furyl CH), 6.33 (dt, J = 6.6, 2.6 Hz, 2 H, furyl CH), 5.7 (s, H, CH=C-S), 4.59 (d, J = 5.8 Hz, 2 H, NH-CH 2 ), 2.49 (s, 3 H, SCH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.9 (Cq, C=O), 69. (Cq, CSMe), 50.4 (Cq, furyl C), 42.6, 0.6, and 08.0 (furyl CH), 40.6 (Cq, i-c of Ph), 30.7, 28.4, and 27. (aromatic CH), 87.4 (CH=C-S), 4. (NH-CH 2 ), 4.7 (SCH 3 ). HRMS (EI) calcd for C 5 H 6 NO 2 S [M+H] + : ; Found: (E)-3-(Benzylamino)-3-(thioethyl)--phenylprop-2-en--one (s): 2.4 g, yield 8%, white solid, m.p.: 4-44 o C. H NMR (400 MHz, CDCl 3 ) δ 2.26 (s, H, NH), 7.87, 7.42, 7.37, and 7.30 (m each, 2:3:4:, aromatic CH), 5.80 (s, H, CH=C-S), 4.63 (d, J = 6.0 Hz, 2 H, NH-CH 2 ), 3.0 (q, J = 7.4 Hz, 2 H, SCH 2 ),.42 (t, J = 7.4 Hz, 3 H, SCH 2 CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.5 (Cq, C=O), 68.7 (Cq, CSMeEt), 40.6 and 37.3 (Cq each), 30.6, 28.8, 28.3, 27.6, 27.4, and 27.0 (aromatic CH), 87.6 (CH=C-S), 47.9 (NH-CH 2 ), 25.9 (SCH 2 ), 3.6 (SCH 2 CH 3 ). HRMS (EI) calcd for C 8 H 9 NOS [M+H] + : ; Found: (E)-3-(Benzylamino)-3-(thiobenzyl)--phenylprop-2-en--one (t): 0.4 g, yield 23%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ 2.05 (s, H, NH), 7.69 and 7.25 (d each, J = 6.5 Hz, 2:3 H, aromatic CH), 7.32, 7.29, 7.22, and 7.8 (m each, :3:4:2 H, aromatic CH), 5.73 (s, H, CH=C-S), 4.50 (d, J = 5.9 Hz, 2 H, NH-CH 2 ), 4.0 (s, 2 H, S-CH 2 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 85.8 (Cq, C=O), 68.2 (Cq, CSBn), 40.5, 37.2, and 34.8 (Cq each), 30.7, 29., 29.0, 28.9, 28.3, S20

21 28., 27.7, 27.4, and 27.0 (aromatic CH), 88.7 (CH=C-S), 48.0 (NH-CH 2 ), 36.6 (SCH 2 ). HRMS (EI) calcd for C 23 H 22 NOS [M+H] + : ; Found: (E)-3-(Diethylamino)-3-(thiomethyl)--p-tolylprop-2-en--one (u): 0.42 g, yield 53%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ 7.73 and 7.5 (d each, J = 8.0 Hz, 2:2 H, aromatic CH), 5.83 (s, H, CH=C-S), 3.53 (q, J = 7. Hz, 4 H, N-CH 2 ), 2.43 (s, 3 H, SCH 3 ), 2.33 (s, 3 H, C 6 H 4 -CH 3 ),.8 (t, J = 7. Hz, 6 H, CH 2 -CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 84. (Cq, C=O), 68.7 (Cq, CSMe), 40.4 and 39.4 (Cq each), 28.6 and 27.3 (aromatic CH), 93.0 (CH=C-S), 46.8 (N-CH 2 ), 2.3 (C 6 H 4 -CH 3 ), 8.0 (SCH 3 ), 3.2 (CH 2 -CH 3 ). HRMS (EI) calcd for C 5 H 22 NOS [M+H] + : ; Found: N-(3-Methyl-3,5-diphenylfuran-2(3H)-ylidene)--phenylmethanamine (3a): 27 mg, yield 75%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.59 (d, J = 7. Hz, 2 H, aromatic CH), 7.45 and 7.29 (d, J = 7.6 Hz, 2:3 H, aromatic CH), 7.33, 7.23, and 7.5 (m each, 3:3:2 H, aromatic CH), 5.86 (s, H, furyl CH), 4.70 (q, J = 5.2 Hz, 2 H, CH 2 ),.76 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.9 (Cq, C=N), 5.6, 43.4, 40.5, and 29.2 (Cq each),29.3, 28.7, 28.5, 28.3, 27.5, 27.0, 26.4, 26.3, and 25.0 (aromatic CH), 08.4 (furyl CH), 52.4 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.0 (CH 3 ). HRMS (EI) calcd for C 24 H 22 NO [M+H] + : ; Found: N-(3-Methyl-3-phenyl-5-p-tolylfuran-2(3H)-ylidene)--phenylmethanamine (3b): 38 mg, yield 78%, pale yellow liquid. H NMR (400 MHz, CDCl 3 ) δ 7.56 (d, J = 8. Hz, 2 H, aromatic CH), 7.53 and 7.22 (d each, J = 7.5 Hz, 2:4 H, aromatic CH), 7.35 (t, J = 6.7 Hz, 3 H, aromatic CH), 7.32 and 7.30 (m each, :2 H, aromatic CH), S2

22 5.88 (s, H, furyl CH), 4.76 (q, J = 5.2 Hz, 2 H, CH 2 ), 2.39 (s, 3 H, C 6 H 4 -CH 3 ),.82 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 66. (Cq, C=N), 5.7, 43.6, 40.6, 39.5, and 26.5 (Cq each), 29.4, 28.6, 28.3, 27.6, 27.0, 26.5, 26.4, and 25.0 (aromatic CH), 07.5 (furyl CH), 52.4 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27. (CH 3 ), 2.5 (C 6 H 4 -CH 3 ). HRMS (EI) calcd for C 25 H 24 NO [M+H] + : ; Found: N-(5-(4-Chlorophenyl)-3-methyl-3-phenylfuran-2(3H)-ylidene)--phenylmet hanamine (3c): 47 mg, yield 79%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.47, 7.27, and 7.7 (d each, J = 8.6 Hz, 2:2: H, aromatic CH), 7.4 (d, J = 7.2 Hz, 2 H, aromatic CH), 7.24 (d, J = 7.8 Hz, 3 H, aromatic CH), 7.2 and 7.3 (m, 2:2 H, aromatic CH), 5.83 (s, H, furyl CH), 4.65 (q, J = 5.2 Hz, 2 H, CH 2 ),.72 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.5 (Cq, C=N), 50.7, 43.3, 40.4, 35.2, and 27.8 (Cq each), 29.0, 28.6, 28.4, 27.5, 27., 26.6, 26.4, and 26.3 (aromatic CH), 09.0 (furyl CH), 52.5 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27. (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOCl [M+H] + : ; Found: N-(3-Methyl-3-phenyl-5-(4-(trifluoromethyl)phenyl)furan-2(3H)-ylidene)--p henylmethanamine (3d): 44 mg, yield 7%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ 7.74 and 7.65 (d each, J = 8.2 Hz, 2:2 H, aromatic CH), 7.50 and 7.27 (d each, J = 7.6 Hz, 2: H, aromatic CH), 7.34 and 7.3 (d each, J = 7. Hz, 3:2 H, aromatic CH), 7.23 (d, J = 6.3 Hz, H, aromatic CH), 7.20 (d, J = 6.7 Hz, H, aromatic CH), 6.05 (s, H, furyl CH), 4.76 (q, J = 5.2 Hz, 2 H, CH 2 ),.83 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.2 (Cq, C=N), 50.4, 43.0, 40.3, and 32.6 (Cq each), 3.0 (q, J = 32.5 Hz, Cq, C-CF 3 ), 24.0 (q, J = Hz, Cq, CF 3 ), 28.7, 28.4, 27.5, 27.3, 26.6, 26.3, 25.7 (q, J = 3.7 Hz, C-C-CF 3 ), and 25.3 S22

23 (aromatic CH), 0.8 (furyl CH), 52.6 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.0 (CH 3 ). HRMS (EI) calcd for C 25 H 2 NOF 3 [M+H] + : ; Found: N-(5-(3-Fluorophenyl)-3-methyl-3-phenylfuran-2(3H)-ylidene)--phenylmeth anamine (3e): 30 mg, yield 73%, pale yellow liquid. H NMR (400 MHz, CDCl 3 ) δ 7.47, 7.39, and 7.25 (d, J = 7.6 Hz, 2:: H, aromatic CH), 7.30, 7.8, and 7.0 (m, 7:2: H, aromatic CH), 5.92 (s, H, furyl CH), 4.7 (q, J = 5.2 Hz, 2 H, CH 2 ),.78 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.3 (Cq, C=N), 63.0 (d, J = Hz, Cq, C-F), 50.5, 43.2, 40.4, and 3.4 (d, J = 8.4 Hz) (Cq each), 30.3 (d, J = 8.4 Hz), 28.6, 28.4, 27.5, 27.2, 26.6, 26.3, 20.8 (d, J = 2.9 Hz), 6.2 (d, J = 2.3 Hz), and 2. (d, J = 23.5 Hz) (aromatic CH), 09.7 (furyl CH), 52.5 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.0 (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOF[M+H] + : ; Found: N-(5-(2-Chlorophenyl)-3-methyl-3-phenylfuran-2(3H)-ylidene)--phenylmet hanamine (3f): 29 mg, yield 69%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.78, 7.60, and 7.49 (d each, J = 7.6 Hz, :2: H, aromatic CH), 7.37 and 7.3 (m, 6:3 H, aromatic CH), 7.23 (d, J = 7.0 Hz, H, aromatic CH), 6.46 (s, H, furyl CH), 4.75 (q, J = 5.3 Hz, 2 H, CH 2 ),.88 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.0 (Cq, C=N), 48., 43.2, 40.5, 32.2, and 27.8 (Cq each), 30.9, 29.9, 29.0, 28.6, 28.4, 27.5, 27., 27.0, 26.5, and 26.4 (aromatic CH), 5.2 (furyl CH), 52.8 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.2 (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOCl [M+H] + : ; Found: N-(3-Methyl-5-(naphthalen-2-yl)-3-phenylfuran-2(3H)-ylidene)--phenylmet hanamine (3g): 26 mg, yield 65%, white solid, m.p.: o C. H NMR (400 S23

24 MHz, CDCl 3 ) δ 8.08 (s, H, aromatic CH), 7.84 and 7.45 (m each, 2: H, aromatic CH), 7.79 and 7.64 (d each, J = 8.5 Hz, : H, aromatic CH), 7.77 (d, J = 2.9 Hz, H, aromatic CH), 7.5, 7.36, 7.2, and 7.7 (d each, J = 7.4 Hz, 2:2:: H, aromatic CH), 7.29 (q, J = 7.9 Hz, 4 H, aromatic CH), 6.00 (s, H, furyl CH), 4.80 (q, J = 5.2 Hz, 2 H, CH 2 ),.82 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.8 (Cq, C=N), 5.7, 43.5, 40.6, 33.7, 33.2, and 26.4 (Cq each), 28.6, 28.5, 28.4, 27.9, 27.6, 27., 26.9, 26.8, 26.5, 26.3, 24.5, and 22.5 (aromatic CH), 09.2 (furyl CH), 52.5 (Cq, C-CH 3 ), 5.5 (CH 2 ), 27. (CH 3 ). HRMS (EI) calcd for C 28 H 24 NO [M+H] + : ; Found: N-(5-(Furan-2-yl)-3-methyl-3-phenylfuran-2(3H)-ylidene)--phenylmethana mine (3h): 09 mg, yield 66%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.55 (d, J = 7.6 Hz, 2 H, aromatic CH), 7.36 and 7.27 (d each, J = 7.4 Hz, 4: H, aromatic CH), 7.32 (t, J = 5.9 Hz, 2 H, aromatic CH), 7.23 (d, J = 4.3 Hz, H, aromatic CH), 7.48 (s), 6.65 (d, J = 3.3 Hz), and 6.48 (s) (:: H, furyl CH), 5.88 (s, H, furyl CH), 4.74 (q, J = 5.3 Hz, 2 H, CH 2 ),.83 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.2 (Cq, C=N), 44.8, 44.0, 43.3, and 40.4 (Cq each), 28.6, 28.3, 27.5, 27., 26.5, and 26.4 (aromatic CH), 43.6,.5, and 09.0 (furyl CH), 07.5 (furyl CH), 5.9 (Cq, C-CH 3 ), 5.3 (CH 2 ), 27.3 (CH 3 ). HRMS (EI) calcd for C 22 H 20 NO 2 [M+H] + : ; Found: N-(3-Methyl-3-phenyl-5-(thiophen-2-yl)furan-2(3H)-ylidene)--phenylmetha namine (3i): 7 mg, yield 68%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.53 and 7.28 (d each, J = 7.5 Hz, 2: H, aromatic CH), 7.37, 7.36, and 7.32 (m each, 2:2:2 H, aromatic CH), 7.35 (d, J = 5.4 Hz, 2 H, thienyl CH), 7.23 (d, J = 6.3 Hz, H, aromatic CH), 7.09 (m, H, thienyl CH), 5.80 (s, H, furyl CH), 4.75 (q, J = 5. Hz, 2 H, CH 2 ),.83 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.5 (Cq, C=N), S24

25 47., 43.4, 40.4, and 32. (Cq each), 28.6, 28.4, 27.6, 27., 26.5, and 26.4 (aromatic CH), 27.8,, 26.6, and 25.7 (thienyl CH), 07.7 (furyl CH), 52.5 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27. (CH 3 ). HRMS (EI) calcd for C 22 H 20 NOS [M+H] + : ; Found: N-(3-Methyl-3,5-diphenylfuran-2(3H)-ylidene)methanamine (3j): 00 mg, yield 76%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.70 (d), 7.44 (t), and 7.40(d) (J = 7.0 Hz, 2:2: H, aromatic CH), 7.49 (d) and 7.26 (t) (J = 7.3 Hz, 2: H, aromatic CH), 7.36 (t, J = 7.6 Hz, 2 H, aromatic CH), 5.9 (s, H, furyl CH), 3.22 (s, 3 H, NCH 3 ),.79 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 66.2 (Cq, C=N), 5.6 and 43.4 (Cq each), 29.3, 28.7, 28.6, 27.0, 26.3, and 25.0 (aromatic CH), 08.4 (furyl CH), 52.2 (Cq, C-CH 3 ), 35.0 (NCH 3 ), 26.6 (CH 3 ). HRMS (EI) calcd for C 8 H 8 NO [M+H] + : ; Found: N-(3-Methyl-3,5-diphenylfuran-2(3H)-ylidene)ethanamine (3k): 02 mg, yield 74%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.67 and 7.49 (d each, J = 7.9 Hz, 2:2 H, aromatic CH), 7.43 (t, J = 7.3 Hz, 2 H, aromatic CH), 7.39 and 7.25 (m each, : H, aromatic CH), 7.35 (t, J = 7.6 Hz, 2 H, aromatic CH), 5.90 (s, H, furyl CH), 3.59 (qd, J = 7.3, 2.2 Hz, 2 H, NCH 2 CH 3 ),.79 (s, 3 H, CH 3 ),.25 (dt, J = 7.3, 3.7 Hz, 3 H, NCH 2 CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 64.8 (Cq, C=N), 5.4, 43.6 and 29.4 (Cq each), 29.3, 28.7, 28.6, 26.9, 26.3, and 25.0 (aromatic CH), 08.5 (furyl CH), 52. (Cq, C-CH 3 ), 42.5 (NCH 2 CH 3 ), 26.7 (CH 3 ), 5.7 (NCH 2 CH 3 ). HRMS (EI) calcd for C 9 H 20 NO [M+H] + : ; Found: N-(5-(3-Methoxyphenyl)-3-methyl-3-phenylfuran-2(3H)-ylidene)ethanamine (3l): 4 mg, yield 74%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.34 and S25

26 6.79 (d each, J = 8.0 Hz, 2: H, aromatic CH), 7.20 (td, J = 7.7, 3. Hz, 3 H, aromatic CH), 7.2 (m, 2 H, aromatic CH), 7.06 (s, H, aromatic CH), 5.75 (s, H, furyl CH), 3.7 (s, 3 H, OCH 3 ), 3.44 (qd, J = 7.3, 2.3 Hz, 2 H, NCH 2 CH 3 ),.64 (s, 3 H, CH 3 ),. (t, J = 7.3 Hz, 3 H, NCH 2 CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 64.7 (Cq, C=N), 59.8 (Cq, C-OCH 3 ), 5.3, 43.5, and 30.7 (Cq each), 29.7, 28.6, 26.9, 26.2, 7.5, 4.8, and 0.6 (aromatic CH), 08.9 (furyl CH), 55.4 (OCH 3 ), 52. (Cq, C-CH 3 ), 42.4 (NCH 2 CH 3 ), 26.6 (CH 3 ), 5.7 (NCH 2 CH 3 ). HRMS (EI) calcd for C 20 H 22 NO 2 [M+H] + : ; Found: (E)-N-(3-Methyl-3,5-diphenylfuran-2(3H)-ylidene)prop-2-en--amine (3m): 08 mg, yield 75%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.56 and 7.40 (d each, J = 8.3 Hz, 2:2 H, aromatic CH), 7.3 (t), 7.27 (d), and 7.4 (t) (J = 7.3 Hz, 2:: H, aromatic CH), 7.23 (t, J = 6.3 Hz, 2 H, aromatic CH), 5.92 (m, H, CH=CH 2 ), 5.8 (s, H, furyl CH), 5.0 and 4.97 (dt each, J = 7.,.8 Hz, : H, CH=CH 2 ), 4.08 (dt, J = 4.4,.8 Hz, 2 H, NCH 2 ),.70 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.9 (Cq, C=N), 5.6, 43.4, and 29.2 (Cq each), 36.0 and 4.9 (CH=CH 2 ), 29.4, 28.7, 28.6, 27.0, 26.3, and 25.0 (aromatic CH), 08.5 (furyl CH), 52.3 (Cq, C-CH 3 ), 50.3 (NCH 2 ), 26.8 (CH 3 ). HRMS (EI) calcd for C 20 H 20 NO [M+H] + : ; Found: (E)-N-(5-(4-Chlorophenyl)-3-methyl-3-phenylfuran-2(3H)-ylidene)prop-2-en- -amine (3n): 24 mg, yield 77%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ 7.5 (d), 7.42 (t), and 7.3 (d) (J = 8.5 Hz, 2:2:2 H, aromatic CH), 7.27 (d, J = 7.8 Hz, 2 H, aromatic CH), 7.8 (t, J = 6.6 Hz, H, aromatic CH), 5.96 (m, H, CH=CH 2 ), 5.84 (s, H, furyl CH), 5.4 and 5.02 (dd each, J = 7.,.6 Hz, : H, CH=CH 2 ), 4. (dd, J = 4.9, 2.0 Hz, 2 H, NCH 2 ),.74 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.4 (Cq, C=N), 50.6, 43.2, 35., and 27.7 (Cq each), 35.9 and 5.0 S26

27 (CH=CH 2 ), 28.9, 28.6, 27., 26.3, and 26.2 (aromatic CH), 08.9 (furyl CH), 52.4 (Cq, C-CH 3 ), 50.3 (NCH 2 ), 26.8 (CH 3 ). HRMS (EI) calcd for C 20 H 9 NOCl [M+H] + : ; Found: N-(3-Methyl-3,5-diphenylfuran-2(3H)-ylidene)butan--amine (3o): 02 mg, yield 67%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.7 (d) and 7.46 (t) (J = 7.2 Hz, 2:2 H, aromatic CH), 7.53 (d) and 7.38 (t) (J = 7.7 Hz, 2:2 H, aromatic CH), 7.42 and 7.29 (m, : H, aromatic CH), 5.93 (s, H, furyl CH), 3.60 (td, J = 7.0, 2.2 Hz, 2 H, NCH 2 ),.82 (s, 3 H, CH 3 ),.68 and.43 (m each, 2:2 H, NCH 2 CH 2 CH 2 ), 0.99 (t, J = 7.4 Hz, 3 H, CH 2 CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 64.7 (Cq, C=N), 5.5, 43.7, and 29.4 (Cq each), 29.3, 28.7, 28.6, 26.9, 26.3, and 25.0 (aromatic CH), 08.4 (furyl CH), 52. (s), 47.6 (NCH 2 ), 32.8 (NCH 2 CH 2 ), 26.8 (CH 3 ), 20.7 (CH 2 CH 3 ), 4. (CH 2 CH 3 ). HRMS (EI) calcd for C 2 H 24 NO [M+H] + : ; Found: N-(3-Methyl-3,5-diphenylfuran-2(3H)-ylidene)octadecan--amine (3p): 48 mg, yield 59%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 7.55 and 7.37 (d, J = 7.3 Hz, 2:2 H, aromatic CH), 7.30 (m, 3 H, aromatic CH), 7.22 (t, J = 7.7 Hz, 2 H, aromatic CH), 7.2 (t, J = 7.0 Hz, H, aromatic CH), 5.78 (s, H, furyl CH), 3.42 (t, J = 7. Hz, 2 H, NCH 2 ),.66 (s, 3 H, CH 3 ),.52 (m, 2 H, NCH 2 CH 2 ),.9 (m, 32 H, CH 2 ), 0.79 (t, J = 6.7 Hz, 3 H, CH 2 CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 64.7 (Cq, C=N), 5.5, 43.7, and 29.5 (Cq each), 29.3, 28.7, 28.6, 26.9, 26.3, and 25.0 (aromatic CH), 08.4 (furyl CH), 52.2 (Cq, C-CH 3 ), 47.9 (NCH 2 ), 32., 30.6, 29.9, 29.8, 29.7, 29.6, 29.5, 27.5, and 22.8 (CH 2 ), 26.8 (CH 3 ), 4.3 (CH 2 CH 3 ). HRMS (EI) calcd for C 35 H 52 NO [M+H] + : ; Found: S27

28 (E)-N-(3-Methyl-3,5-diphenylfuran-2(3H)-ylidene)cyclohexanamine (3q): 89 mg, yield 54%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.66 (d) and 7.34 (t) (J = 7.6 Hz, 2:2 H, aromatic CH), 7.5 (d, J = 7.9 Hz, 2 H, aromatic CH), 7.43 (t) and 7.38 (d) (J = 7. Hz, 2: H, aromatic CH), 7.24 (m, H, aromatic CH), 5.89 (s, H, furyl CH), 3.88 (m, H, NCH),.87,.82,.68,.50,.4, and.27 (m each, :2::2:2:2 H, cyclohex CH),.78 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 63. (Cq, C=N), 5.0, 43.9, and 29.5 (Cq each), 29.2, 28.6, 28.5, 26.8, 26.3, and 25.0 (aromatic CH), 08.6 (furyl CH), 56.3 (NCH), 52.0 (Cq, C-CH 3 ), 33.9, 33.7, 26.0, and 25. (CH 2 ), 27. (CH 3 ). HRMS (EI) calcd for C 23 H 26 NO [M+H] + : ; Found: (E)--(Furan-2-yl)-N-(3-methyl-3,5-diphenylfuran-2(3H)-ylidene)methanami ne (3r): 30 mg, yield 79%, white solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 7.68 (dd, J = 8.2,.4 Hz, 2 H, aromatic CH), 7.5 (d), 7.43 (t), and 7.35 (d) (J = 7.2 Hz, 2:2:2 H, aromatic CH), 7.40 and 7.33 (m each, : H, aromatic CH), 7.26 (t, J = 3.7 Hz, H, furyl CH), 6.32 (dd, J = 3.,.9 Hz, H, furyl CH), 6.8 (dd, J = 3., 0.8 Hz, H, furyl CH), 5.95 (s, H, furyl CH), 4.73 (m, 2 H, NCH 2 ),.82 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 66.9 (Cq, C=N), 53.9, 5.6, 43.2, and 29.2 (Cq each), 4.6, 0.3, 08.7, and 06.2 (furyl CH), 29.4, 28.7, 28.6, 27., 26.3, and 25. (aromatic CH), 52.6 (Cq, C-CH 3 ), 45.2 (NCH 2 ), 26.9 (CH 3 ). HRMS (EI) calcd for C 22 H 20 NO 2 [M+H] + : ; Found: N-(3-(2-Fluorophenyl)-3-methyl-5-phenylfuran-2(3H)-ylidene)--phenylmeth anamine (3s): 93 mg, yield 52%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.66 (d, J = 7. Hz, 2 H, aromatic CH), 7.6 (t, J = 8.0 Hz, H, aromatic CH), 7.45, 7.4, 7.35 (d each), and 7. (t) (J = 7.6 Hz, 2:2:2: H, aromatic CH), 7.38, 7.27, 7.23, and S28

29 7.05 (m each, ::: H, aromatic CH), 6.0 (d, J = 2.0 Hz, H, furyl CH), 4.86 (s, 2 H, CH 2 ),.85 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65. (Cq, C=N), 6.2 (d, J = Hz, Cq, C-F), 5.9, 40.5, 29.8, and 29.3 (d, J =.5 Hz) (Cq each), 29.4, 28.9 (d, J = 8.7 Hz), 28.7, 28.4, 27.8, 27.6 (d, J = 3.9 Hz), 26.7, 25., 24.2 (d, J = 3.4 Hz), and 6.2 (d, J = 22.5 Hz) (aromatic CH), 07.3 (d, J = 4.2 Hz, furyl CH), 5.7 (CH 2 ), 50.4 (Cq, C-CH 3 ), 26.3 (d, J =.3 Hz, CH 3 ). HRMS (EI) calcd for C 24 H 2 NOF [M+H] + : ; Found: N-(3-(3-Fluorophenyl)-3-methyl-5-phenylfuran-2(3H)-ylidene)--phenylmeth anamine (3t): 2 mg, yield 63%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.70 and 7.27 (d each, J = 6.8 Hz, 2: H, aromatic CH), 7.46 (t) and 7.40 (d) (J = 7. Hz, 2:2 H, aromatic CH), 7.42 (d, J = 7.4 Hz, H, aromatic CH), 7.35, 7.30, and 6.97 (m each, 3:2: H, aromatic CH), 5.95 (s, H, furyl CH), 4.80 (q, J = 5.2 Hz, 2 H, CH 2 ),.84 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.3 (Cq, C=N), 63.0 (d, J = Hz, Cq, C-F), 52.0, 46. (d, J = 6.9 Hz), 40.4, and 29.0 (Cq each), 30.0 (d, J = 8.2 Hz), 29.6, 28.8, 28.4, 27.6, 26.6, 25., 22. (d, J = 2.8 Hz), 4.0 (d, J = 2. Hz), and 3.7 (d, J = 22.6 Hz) (aromatic CH), 07.7 (furyl CH), 52.2 (d, J =.7 Hz, Cq, C-CH 3 ), 5.5 (CH 2 ), 27.2 (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOF [M+H] + : ; Found: N-(3-Methyl-5-phenyl-3-(3-(trifluoromethyl)phenyl)furan-2(3H)-ylidene)--p henylmethanamine (3u): 8 mg, yield 58%, yellow liquid. H NMR (400 MHz, CDCl 3 ) δ 7.7 (s, H, aromatic CH), 7.6 and 7.39 (d each, J = 7.8 Hz, : H, aromatic CH), 7.56 (d, J = 6.8 Hz, 2 H, aromatic CH), 7.30 (m, 4 H, aromatic CH), 7.24 (d) and 7.0 (t) (J = 7.2 Hz, 2: H, aromatic CH), 7.9 (t, J = 7.5 Hz, 2 H, aromatic CH), 5.83 (s, H, furyl CH), 4.65 (s, 2 H, CH 2 ),.7 (s, 3 H, CH 3 ). 3 C{ H} S29

30 NMR (00 MHz, CDCl 3 ) δ 65.0 (Cq, C=N), 52.3, 44.6, 40.3, and 28.9 (Cq each), 30.8 (q, J = 32. Hz, Cq, C-CF 3 ), 30.0, 29.7, 29.0, 28.8, 28.4, 27.6, 26.7, 25.2, 24.0 (dd, J = 7.5, 3.7 Hz), and 23.3 (dd, J = 7.8, 3.9 Hz) (aromatic CH), 24.3 (q, J = Hz, Cq, CF 3 ), 07.2 (furyl CH), 52.3 (Cq, C-CH 3 ), 5.5 (CH 2 ), 27.6 (CH 3 ). HRMS (EI) calcd for C 25 H 2 NOF 3 [M+H] + : ; Found: N-(3-(4-Fluorophenyl)-3-methyl-5-phenylfuran-2(3H)-ylidene)--phenylmeth anamine (3v): 46 mg, yield 82%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.64 (d) and 7.9 (t) (J = 6.9 Hz, 2: H, aromatic CH), 7.47, 7.45, and 7.30 (d each, J = 5.2 Hz, ::2 H, aromatic CH), 7.40 and 7.28 (m each, : H, aromatic CH), 7.38 (d, J = 7.5 Hz, H, aromatic CH), 7.34 (d, J = 6.4 Hz, 2 H, aromatic CH), 6.98 (t, J = 8.7 Hz, 2 H, aromatic CH), 5.89 (s, H, furyl CH), 4.72 (q, J = 5. Hz, 2 H, CH 2 ),.77 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.7 (Cq, C=N), 6.9 (d, J = Hz, Cq, C-F), 5.8, 40.4, 39.3 (d, J = 3. Hz), and 29. (Cq each), 29.5, 28.7, 28.4, 28. (d, J = 8.0 Hz), 27.5, 26.6, 25., and 5.3 (d, J = 2.3 Hz) (aromatic CH), 08.0 (furyl CH), 5.9 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.3 (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOF [M+H] + : ; Found: N-(3-(4-Chlorophenyl)-3-methyl-5-phenylfuran-2(3H)-ylidene)--phenylmet hanamine (3w): 49 mg, yield 80%, yellow solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 7.66 (d, J = 8. Hz, 2 H, aromatic CH), 7.45 (d, J = 8.6 Hz, 2 H, aromatic CH), 7.42, 7.38, and 7.28 (m each, 2:: H, aromatic CH), 7.33 and 7.30 (d each, J = 4.4 Hz, 2:2 H, aromatic CH), 7.22 (t, J = 7.3 Hz, 2 H, aromatic CH), 5.90 (s, H, furyl CH), 4.74 (q, J = 5.2 Hz, 2 H, CH 2 ),.79 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.4 (Cq, C=N), 52.0, 42., 40.4, 32.9, and 29.0 (Cq S30

31 each), 29.6, 28.7, 28.6, 28.4, 27.9, 27.6, 26.6, and 25. (aromatic CH), 07.7 (furyl CH), 5.9 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.3 (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOCl [M+H] + : ; Found: N-(3-(4-Bromophenyl)-3-methyl-5-phenylfuran-2(3H)-ylidene)--phenylmeth anamine (3x): 50 mg, yield 72%, yellow solid, m.p.: o C. H NMR (400 MHz, CDCl 3 ) δ 7.59 (d, J = 6.9 Hz, 2 H, aromatic CH), 7.37 (d, J = 8.7 Hz, 3 H, aromatic CH), 7.34, 7.30, and 7.27 (d each, J = 4.8 Hz, 2::2 H, aromatic CH), 7.32 (m, 2 H, aromatic CH), 7.23 (d, J = 7.8 Hz, H, aromatic CH), 7.6 (d, J = 7. Hz, H, aromatic CH), 5.83 (s, H, furyl CH), 4.68 (q, J = 5.2 Hz, 2 H, CH 2 ),.72 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.0 (Cq, C=N), 52.0, 42.6, 40.3, 29.0, and 2. (Cq each), 3.6, 29.6, 28.7, 28.4, 28.2, 27.6, 26.6, and 25. (aromatic CH), 07.6 (furyl CH), 52.0 (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.2 (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOBr [M+H] + : ; Found: N-(3-(4-Iodophenyl)-3-methyl-5-phenylfuran-2(3H)-ylidene)--phenylmetha namine (3y): 46 mg, yield 63%, colorless liquid. H NMR (400 MHz, CDCl 3 ) δ 7.62 (t, J = 7. Hz, 4 H, aromatic CH), 7.40 and 7.9 (m each, : H, aromatic CH), 7.36 and 7.24 (d each, J = 8.5 Hz, 2:2 H, aromatic CH), 7.33 (d, J = 4.2 Hz, H, aromatic CH), 7.30 (d, J = 4.7 Hz, 2 H, aromatic CH), 7.27 (d, J = 7.9 Hz, H, aromatic CH), 5.86 (s, H, furyl CH), 4.7 (q, J = 5.2 Hz, 2 H, CH 2 ),.75 (s, 3 H, CH 3 ). 3 C{ H} NMR (00 MHz, CDCl 3 ) δ 65.2 (Cq, C=N), 52.0, 43.3, 40.3, and 29.0 (Cq each), 37.6, 29.6, 28.7, 28.5, 28.4, 27.6, 26.6, and 25. (aromatic CH), 07.6 (furyl CH), 92.7 (Cq, C-I), 52. (Cq, C-CH 3 ), 5.4 (CH 2 ), 27.2 (CH 3 ). HRMS (EI) calcd for C 24 H 2 NOI [M+H] + : ; Found: S3