Supporting Information. for. Z-Selective Synthesis of γ,δ-unsaturated Ketones via Pd-Catalyzed

Supporting Information for Z-Selective Synthesis of γ,δ-unsaturated Ketones via Pd-Catalyzed Ring Opening of 2-Alkylenecyclobutanones with Arylboronic Acids Yao Zhou, Changqing Rao, and Qiuling Song *,, Institute of Next Generation Matter Transformation, College of Chemical Engineering and College of Material Sciences Engineering at Huaqiao University, 668 Jimei Blvd, Xiamen, Fujian 361021, P. R. China National Laboratory for Molecular Sciences, Institute of Chemistry, CAS, Beijing 100190, P. R. China fax:86-592-6162990; email: qsong@hqu.edu.cn 1

Table of Contents 1. General information...3 2. Optimization of experiment conditions...4 3. General procedure for starting materials...6 4. General process for the synthesis of ketones 3...6 5. Determination stereochemistry of the products...7 6. Other boron reagents of this transformation...7 7. Preliminary mechanistic studies...8 8. Characterization data for products......10 9. NMR spectroscopic data... 28 2

1. General information All chemicals were purchased from Adamas Reagent, Ltd, energy chemical company, J&K Scientific Ltd, Alfa Aesa chemical company and so forth. All reagents and solvents were purchased from commercial suppliers and used without further purification. Unless otherwise stated, all experiments were conducted in a Schlenk tube under N 2 atmosphere. Reactions were monitored by TLC or GC-MS analysis. Flash column chromatography was performed over silica gel (200-300 mesh). 1 H-NMR and 13 C-NMR spectra were recorded in CDCl 3 on a Bruker Avance 500 spectrometer (500 MHz 1 H, 125 MHz 13 C) at room temperature. Chemical shifts were reported in ppm on the scale relative to CDCl 3 (δ = 7.26 for 1 H-NMR, δ = 77.00 for 13 C-NMR) as an internal reference. High resolution mass spectra were recorded using a Thermo Fisher Scientific LTQ FT Ultra or Waters Micromass GCT Premier instrument. Coupling constants (J) were reported in Hertz (Hz). 3

2. Optimization of experiment conditions Table S1. Optimization of the reaction with different ligands 4

Table S2. Optimization of the reaction with different bases and Pd salts 5

3. General procedure for the synthesis of 2-alkylenecyclobutanones 1 In a dried Schlenk tube was placed Ca(OH) 2 (37 mg, 0.5 mol, 0.1 equiv). Then, corresponding benzaldehydes (5 mol, 1.0 equiv) and cyclobutanone (15 mol, 1.05 g, 3.0 equiv) in anhydrous ethanol (15 ml) were added at N 2 atmosphere. The resulting mixture was stirred at 80 o C for 24 h. Upon completion of the reaction, the solvent was evaporated under vacuum and the residue was purified through flash column chromatogram petroleum ether:acoet (20:1, v/v) as the eluent to afford the desired cyclobutanones. This method was according to the previous literature. 1 A representative example: (E)-2-benzylidenecyclobutanone (1a), yellow soild. 1 H NMR (500 MHz, CDCl 3 ): δ = 7.52 (d, J = 7.9 Hz, 2H), 7.46-7.36 (m, 3H), 7.04 (t, J = 2.8 Hz,1H), 3.15 (t, J = 6.4 Hz, 2H), 3.00 (dt, J = 7.8 Hz, 2.8 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ): δ = 199.6, 146.2, 134.5, 130.1, 130.0, 128.9, 126.4, 45.8, 23.5. 4. General process for the synthesis of γ,δ-unsaturated ketones 3 Arylboronic acids 2 (0.3 mmol) was added to a mixture of 2-alkylenecyclobutanones 1 (0.2 mmol), Pd 2 (dba) 3 (9.15 mg, 5 mol %), PCy 3 (5.6 mg, 10 mol %) and K 2 CO 3 (27.6 mg, 1.0 equiv) in 1,4-dioxane (2 ml). Then the Schlenk tube was evacuated with N 2 three times. The resulting mixture was stirred at 100 C for 22 h. Upon completion of the reaction, the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatograph (silica gel, petroleum ether:acoet = 100:1, v/v) to give the desired product 3. 1 L. Yu, Y. Wu, H. Cao, X. Zhang, X. Shi, J. Luan, T. Chen, Y. Pan and Q. Xu, Green Chem., 2014, 16, 287. 6

5. Determination Stereochemistry of the Products The comparison of two different configurations E-3aa vs Z-3aa = 6.31 (dt, J = 15.8, 6.9 Hz, 1H) vs 5.73 (dt, J = 11.6, 7.3 Hz, 1H) (chemical shift and coupling constants of H 1 ) E-3aa vs Z-3aa = 27.5 vs 23.2 (chemical shift of C 1 ) The products (Z)-3aa and (E)-3aa had been reported by the literatures (Chem. Commun. 2004, 2598-2599 and Org. Biomol. Chem. 2006, 4, 3102-3107). Comparing the NMR spectra and chemical shifts of the corresponding products (Z)-3aa and (E)-3aa, we could also determine the stereochemistry of the product which we obtained was (Z)-configuration. 6. Other boron reagents of this transformation 7

7. Preliminary mechanistic studies 7.1 Control experiments When the reaction was performed in the absence of phenylboronic acid (2a), (E)-2-benzylidenecyclobutanone (1a) still stayed intact and no decarbonylation product was detected by GC-MS (Eq S1), indicating that the Pd(0) might not insert into the cyclobutanone under the basic conditions. When phenylboronic acid (2a) was conducted in the standard conditions without (E)-2-benzylidenecyclobutanone (1a), it turned out that the 1,1'-biphenyl was the major product (Eq S2). The formation of 1,1'-biphenyl suggest that a Pd(II) species might exist in this transformation. 7.2 Labeling Experiments When the reaction was performed in the absence of phenylboronic acid (2a) and 3eq D 2 O was added under the standard conditions. The result turned out deuterium was incorporated at the C(sp 3 ) adjacent to the carbonyl group of starting material 1a ( Eq S3). 8

1 H NMR Spectra of deuterated 1a When the model reaction was carried out in 3eq D 2 O under the standard conditions, deuterium was incorporated both at the α and γ-position of the produced (Z)-1,5-diphenylpent-4-en-1-one (Eq S4). 9

1 H NMR Spectra of deuterated 3aa 8. Characterization data for the products (Z)-1,5-diphenylpent-4-en-1-one (3aa) (CAS: 821770-37-0) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (silica gel, petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow oil (44.8 mg, 95%), Selectivity (Z/E) = 95:5. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.96 (d, J = 7.1 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 7.37 7.29 (m, 4H), 7.24 (t, J = 7.0 Hz, 1H), 6.49 (d, J = 11.6 Hz, 1H), 5.73 (dt, J = 11.6, 7.3 Hz, 1H), 3.12 (t, J = 7.5 Hz, 2H), 2.79 (qd, J = 7.4, 1.7 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.3, 137.2, 136.8, 133.0, 130.9, 129.9, 128.7, 128.6 128.2, 128.0, 126.7, 38.6, 23.2. 10

(Z)-1-phenyl-5-(p-tolyl)pent-4-en-1-one (3ba) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow oil (48 mg, 96%), Selectivity (Z/E)= 99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.96 (d, J = 7.1 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 6.45 (d, J = 11.6 Hz, 1H), 5.67 (dt, J = 11.6, 7.3 Hz, 1H), 3.12 (t, J = 7.5 Hz, 2H), 2.79 (qd, J = 7.4, 1.7 Hz, 2H), 2.35 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.4, 136.9, 136.4, 134.4, 133.0, 130.2, 129.8, 128.9, 128.6, 128.6, 128.0, 38.7, 23.3, 21.1. HRMS (EI, m/z) calcd for [C 18 H 18 O]: 250.1354; found: 250.1358. (Z)-1-phenyl-5-(m-tolyl)pent-4-en-1-one (3ca) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow oil (43.5 mg, 87%), Selectivity (Z/E)= 94:6. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.96 (d, J = 7.2 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 7.23 (t, J = 7.5 Hz, 1H), 7.12 (d, J = 9.2 Hz, 2H), 7.05 (d, J = 7.4 Hz, 1H), 6.46 (d, J = 11.6 Hz, 1H), 5.70 (dt, J = 11.6, 7.3 Hz, 1H), 3.12 (t, J = 7.5 Hz, 2H), 2.79 (qd, J = 7.4, 1.7 Hz, 2H), 2.35 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ 199.3, 137.7, 137.2, 136.9, 133.0, 130.7, 130.0, 129.5, 128.6, 128.1, 128.0, 127.5, 125.8, 38.6, 23.3, 21.4. HRMS (ESI, m/z) calcd for [C 18 H 18 O+H + ]: 251.1430; found: 251.1436. 11

(Z)-1-phenyl-5-(o-tolyl)pent-4-en-1-one (3da) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow oil (46.5 mg, 93%), Selectivity (Z/E) > 99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.94 (d, J = 7.1 Hz, 2H), 7.56 (tt, J = 7.5 Hz, 1.5 Hz, 1H), 7.45 (t, J = 7.7 Hz, 2H), 7.24 7.15 (m, 4H), 6.52 (d, J = 11.4 Hz, 1H), 5.80 (dt, J = 11.4, 7.4 Hz, 1H), 3.06 (t, J = 7.5 Hz, 2H), 2.61 (qd, J = 7.4, 1.6 Hz, 2H), 2.27 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.3, 136.8, 136.3, 136.2, 133.0, 130.7, 129.8, 129.2, 128.9, 128.5, 128.0, 126.9, 125.4, 38.6, 23.1, 19.8. HRMS (EI, m/z) calcd for [C 18 H 18 O]: 250.1369; found: 250.1358. (Z)-5-(4-methoxyphenyl)-1-phenylpent-4-en-1-one (3ea) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 45:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (49.4 mg, 95%), Selectivity (Z/E) = 97:3. 1 H NMR (500 MHz, CDCl 3 ) δ =7.96 (d, J = 7.1 Hz, 2H), 7.56 (tt, J = 7.5 Hz, 1.5 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H), 6.88 (dt, J = 8.5, 2.0 Hz, 2H), 6.42 (d, J = 11.6 Hz, 1H), 5.62 (dt, J = 11.6, 7.2 Hz, 1H), 3.81 (s, 3H), 3.12 (t, J = 7.5 Hz, 2H), 2.78 (qd, J = 7.4, 1.6 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ =199.4, 158.3, 136.9, 133.0, 129.9, 129.3, 129.3, 128.6, 128.0, 127.1, 113.6, 55.2, 38.7, 23.3. HRMS (ESI, m/z) calcd for [C 18 H 18 O 2 +H + ]: 267.1380; found: 267.1385. 12

(Z)-5-(4-fluorophenyl)-1-phenylpent-4-en-1-one (3fa) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 70:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow solid (46.7 mg, 92%), Selectivity (Z/E) = 93:7. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.95 (d, J = 7.1 Hz, 2H), 7.56 (tt, J = 7.5, 1.0 Hz,1H), 7.46 (t, J = 7.7 Hz, 2H), 7.26 (t, J = 7.0 Hz, 2H), 7.02 (t, J = 8.7 Hz, 2H), 6.43 (d, J = 11.6 Hz, 1H), 5.69 (dt, J = 11.6, 7.3 Hz, 1H), 3.12(t, J = 7.5 Hz, 2H), 2.75 (qd, J = 7.3, 1.8 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ =199.2, 161.6 (d, J C-F = 246.9 Hz), 136.8, 133.1, 130.8, 130.8 (d, J C-F = 2.3 Hz), 130.3, 130.2, 128.8, 128.6, 128.0, 115.1 (d, J C-F = 21.3 Hz), 38.5, 23.1. HRMS (ESI, m/z) calcd for [C 17 H 15 FO+H + ]: 255.1180; found: 255.1185. (Z)-5-(4-(tert-butyl)phenyl)-1-phenylpent-4-en-1-one (3ga) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 70:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow oil (56.2 mg, 98%), Selectivity (Z/E) > 99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.97 (d, J = 7.5 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.46 (t, J = 7.7 Hz, 2H), 7.37 (d, J = 8.3 Hz, 2H), 7.27 (d, J = 8.5 Hz, 2H), 6.47 (d, J = 11.6 Hz, 1H), 5.69 (dt, J = 11.6, 7.3 Hz, 1H), 3.13 (t, J = 7.5 Hz, 2H)), 2.82 (qd, J = 7.5, 1.6 Hz, 2H), 1.34 (s, 9H). 13 C NMR (125 MHz, CDCl 3 ) δ= 199.4, 149.6, 136.9, 134.4, 133.0, 130.3, 129.7, 128.6, 128.5, 128.0, 125.1, 38.7, 34.5, 31.3, 23.3. HRMS (ESI, m/z) calcd for [C 21 H 24 O+H + ]: 293.1900; found: 293.1905. 13

(Z)-N-(4-(5-oxo-5-phenylpent-1-en-1-yl)phenyl)acetamide (3ha) The reaction was performed following the general procedure on 0.1 mmol scale. The residue was purified by flash column chromatograph (petroleum ether:acoet = 2:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow solid (48.6 mg, 83%), Selectivity (Z/E) = 90:10. 1 H NMR (500 MHz, CDCl 3 ) δ =7.95 (d, J = 7.1 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.47-7.44 (m, 4H), 7.25 (d, J = 8.3 Hz, 2H), 6.41 (d, J = 11.7 Hz, 1H), 5.66 (dt, J = 11.6, 7.2 Hz, 1H), 3.11 (t, J = 7.4 Hz, 2H), 2.77 (qd, J = 7.3, 1.7 Hz, 2H), 2.17 (s, 3H). 13 C NMR (126 MHz, CDCl 3 ) δ =199.4, 168.3, 136.8, 136.5, 133.4, 133.1, 130.5, 129.4, 129.3, 128.6 128.0, 119.6, 38.6, 24.6, 23.3. HRMS (ESI, m/z) calcd for [C 19 H 19 NO 2 +H + ]:294.1490; found:294.1494. (Z)-1-phenyl-5-(thiophen-2-yl)pent-4-en-1-one (3ia) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 70:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (46.9 mg, 97%), Selectivity (Z/E) = 57:43. (Z): 1 H NMR (500 MHz, CDCl 3 ) δ = 7.98-7.97 (m, 2H (E-3ia), 2H (Z-3ia)), 7.57 (t, J = 6.8 Hz, 1H (E-3ia), 1H (Z-3ia)), 7.47 (t, J = 7.7 Hz, 2H (E-3ia), 2H (Z-3ia)), 7.26 (d, J = 5.1 Hz, 1H (E-3ia)), 7.01 (d, J = 3.5 Hz, (Z-3ia)), 6.93 (d, J = 5.1 Hz, 1H (E-3ia)), 6.89 (d, J = 3.4 Hz, 1H (Z-3ia)), 6.60 (d, J = 13.6 Hz, 1H (E-3ia)), 6.58 (d, J = 3.3 Hz, 1H (Z-3ia)), 6.14 (dt, J = 16.0, 7.5 Hz, 1H (E-3ia)), 5.65 (dt, J = 11.4, 7.5 Hz, 1H (Z-3ia)), 3.20 (t, J = 7.5 Hz, 2H (E-3ia)), 3.15 (t, J = 7.5 Hz, 2H (Z-3ia)), 2.87 (qd, J = 7.3 Hz, 1.7 Hz, 2H (E-3ia)). 2.63 (qd, J = 7.3, 1.7 Hz, 2H (Z-3ia)). (Z and E) 13 C NMR (125 MHz, CDCl 3 ) δ = 199.1, 199.1, 142.6, 140.2, 136.8, 133.1, 129.0, 128.9, 14

128.6, 128.0, 128.0, 127.4, 127.2, 126.8, 125.2, 124.6, 124.1, 123.4, 122.7, 38.1, 38.0, 27.3, 23.8. HRMS (EI, m/z) calcd for [C 15 H 14 OS]: 242.0771; found: 242.0765. (Z)-5-(4-(benzo[b]thiophen-3-yl)phenyl)-1-phenylpent-4-en-1-one (3ja) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 70:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (56.1 mg, 96%), Selectivity (Z/E) = 60:40. (Z): 1 H NMR (500 MHz, CDCl 3 ) δ = δ = 8.01 (dd, J = 8.3, 1.2 Hz, 2H (Z-3ja)), 7.94 (dd, J = 8.3, 1.2 Hz, 2H (E-3ja)), 7.87 (dd, J = 7.2, 1.2 Hz, 2H (Z-3ja)), 7.77 (dd, J = 7.2, 1.2 Hz, 2H (E-3ja)), 7.55 (t, J = 7.5 Hz, 1H (Z-3ja), 1H (E-3ja)), 7.51 7.43 (m, 2H (Z-3ja), 2H (E-3ja)), 7.42 7.33 (m, 3H (Z-3ja), 3H (E-3ja)), 6.74 (d, J = 16.5, 1H (E-3ja)), 6.64 (d, J = 11.4 Hz, 1H (Z-3ja)), 6.37 (dt, J = 15.8, 7.0 Hz, 1H (E-3ja)), 5.94 (dt, J = 11.4, 7.2 Hz, 1H (Z-3ja)), 3.21 (t, J = 7.3 Hz, 2H (E-3ja)), 3.14 (t, J = 7.3 Hz, 2H (Z-3ja)), 2.81 (qd, J = 7.3, 1.7 Hz, 2H (Z-3ja)), 2.74 (qd, J = 7.0, 1.0 Hz, 2H (E-3ja)). (Z and E) 13 C NMR (125 MHz, CDCl 3 ) δ = 199.3, 199.3, 140.3, 139.6, 138.9, 137.8, 136.9, 136.8, 134.1, 133.1, 133.1, 132.9, 132.2, 131.0, 128.6, 128.6, 128.0, 128.0, 124.4, 124.3, 124.1, 124.1, 123.5, 123.1, 122.8, 122.6, 122.0, 121.9, 121.9, 121.0, 38.4, 38.2, 27.8, 23.9. HRMS (EI, m/z) calcd for [C 19 H 16 OS]: 292.0935; found: 292.0922. (Z)-5-(furan-2-yl)-1-phenylpent-4-en-1-one (3ka) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 70:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (42.4 mg, 94%), Selectivity (Z/E) = 99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.99 (dd, J = 8.3, 1.3 Hz, 2H), 7.56 (tt, J = 7.5, 1.0 Hz 1H), 7.46 (t, J = 7.7 Hz, 2H), 15

7.37 (d, J = 1.6 Hz, 1H), 6.39 (dd, J = 3.3, 1.8 Hz, 1H), 6.30 (d, J = 3.3 Hz, 1H), 6.23 (d, J = 11.7 Hz, 1H), 5.62 (dt, J = 11.7, 7.5 Hz, 1H), 3.17 (t, J = 7.4 Hz, 2H), 2.91 (qd, J = 7.5, 1.6 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.5, 153.0, 141.5, 136.9, 133.0, 128.8, 128.5, 128.0, 118.1, 111.1, 109.3, 38.3, 23.9. HRMS (ESI, m/z) calcd for [C 15 H 14 O 2 +H + ]: 227.1067; found: 227.1072. (E)-5-(naphthalen-1-yl)-1-phenylpent-4-en-1-one (3la) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow solid (45.8 mg, 80%), Selectivity (Z/E) = 94:6. 1 H NMR (500 MHz, CDCl 3 ) δ = 8.02 7.98 (m, 1H), 7.90 7.83 (m, 3H), 7.78 (d, J = 8.3 Hz, 1H), 7.55 7.48 (m, 3H), 7.47 7.36 (m, 4H), 6.96 (d, J = 11.4 Hz, 1H), 6.03 (dt, J = 11.4, 7.4 Hz, 1H), 3.04 (t, J = 7.3 Hz, 2H), 2.61 (qd, J = 7.4, 1.6 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ =199.3 136.8, 134.4, 133.5, 132.9, 132.5, 131.8, 128.5,128.3, 128.3, 128.0, 127.3, 126.3, 125.8,125.7, 125.2, 124.9, 38.6, 23.5. HRMS (ESI, m/z) calcd for [C 21 H 18 O+H + ]: 287.1431; found: 287.1436. (Z)-5-phenyl-1-(p-tolyl)pent-4-en-1-one (3ab) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (48.5 mg, 97%), Selectivity (Z/E) = 92:8. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.86 (d, J = 8.2 Hz, 2H), 7.36 7.28 (m, 4H), 7.23 (t, J = 7.4 Hz, 2H), 6.48 (d, J = 11.6 Hz, 1H), 5.72 (dt, J = 11.6, 7.3 Hz, 1H), 3.09 (t, J = 7.5 Hz, 2H), 2.78 (qd, J = 6.5, 0.5 Hz, 2H), 2.41 (s, 3H). 13 C NMR (125 MHz, 16

CDCl 3 ) δ = 199.0, 143.8, 137.3, 134.4, 131.0, 129.9, 129.2, 128.7, 128.2, 128.1, 126.7, 38.5, 23.3, 21.6. HRMS (EI, m/z) calcd for [C 18 H 18 O]: 250.1359; found: 250.1358. (Z)-1-(4-methoxyphenyl)-5-phenylpent-4-en-1-one (3ac) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 45:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (52.1 mg, 98%), Selectivity (Z/E) > 99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.94 (d, J = 8.9 Hz, 2H), 7.36 7.28 (m, 4H), 7.22 (t, J = 8.6, Hz, 1H), 6.92 (d, J = 8.9 Hz, 2H), 6.47 (d, J = 11.6 Hz, 1H), 5.72 (dt, J = 11.6, 7.3 Hz, 1H), 3.86 (s, 3H), 3.06 (t, J = 7.5, Hz, 2H), 2.77 (qd, J = 7.4, 1.7 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ = 197.8, 163.4, 137.2, 131.1, 130.2, 129.8, 128.9, 128.7, 128.2, 126.6, 113.7, 55.4, 38.2, 23.4. HRMS (EI, m/z) calcd for [C 18 H 18 O 2 ]: 266.1312; found: 266.1307. (Z)-1-(4-(tert-butyl)phenyl)-5-phenylpent-4-en-1-one (3ad) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 60:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (54.3 mg, 93%), Selectivity (Z/E) = 97:3. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.90 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 7.35-7.30 (m, 4H), 7.23 (dt, J = 7.0, 2.0 Hz, 1H), 6.48 (d, J = 11.6 Hz, 1H), 5.72 (dt, J = 11.6, 7.3 Hz, 1H), 3.10 (m, J = 8.0 Hz, 2H), 2.78 (qd, J = 7.4, 1.7 Hz, 2H), 1.34 (s, 9H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.0, 156.7, 137.3, 134.3, 131.1, 129.9, 128.7, 128.2, 128.0, 126.7, 125.5, 38.5, 35.0, 31.1, 23.3. HRMS (ESI, m/z) calcd for [C 21 H 24 O+H + ]: 293.1899; found: 293.1905. 17

(Z)-5-phenyl-1-(4-propylphenyl)pent-4-en-1-one (3ae) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 60:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (47.8 mg, 86%), Selectivity (Z/E) >99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.88 (d, J = 8.3 Hz, 2H), 7.36 7.29 (m, 4H), 7.26 (d, J = 2.7 Hz, 1H), 7.23 (t, J = 7.0 Hz, 2H), 6.48 (d, J = 11.6 Hz, 1H), 5.72 (dt, J = 11.6, 7.3 Hz, 1H), 3.10 (t, J = 7.5 Hz, 2H), 2.78 (qd, J = 7.4, 1.8 Hz, 2H), 2.64 (t, J = 7.5 Hz, 2H), 1.70-1.63 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.0, 148.5, 137.3, 134.5, 131.1, 129.8, 128.7, 128.7, 128.2, 128.1, 126.7, 38.5, 38.0, 24.2, 23.3, 13.8. HRMS (EI, m/z) calcd for [C 20 H 22 O]: 278.1678; found: 278.1671. (Z)-1-(3,5-dimethylphenyl)-5-phenylpent-4-en-1-one (3af) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 60:1, v/v) to give the product as a mixture of Z/E-isomers as a white solid (42.4 mg, 81%), Selectivity (Z/E) = 93:7. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.59 (d, J = 7.5 Hz, 2H), 7.38 7.28 (m, 4H), 7.24 (tt, J = 7.0, 2.0 Hz, 1H), 7.20 (d, J = 7.5 Hz, 1H), 6.49 (d, J = 11.6 Hz, 1H), 5.73 (dt, J = 11.6, 7.3 Hz, 1H), 3.10 (d, J = 8.0 Hz, 2H), 2.79 (qd, J = 7.4, 1.7 Hz, 2H), 2.38 (s, 6H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.7, 138.1, 137.3, 136.9, 134.6, 131.0, 129.8, 128.7, 128.2, 126.6, 125.8, 38.7, 23.3, 21.2. HRMS (EI, m/z) calcd for [C 19 H 20 O]: 264.1506; found: 264.1514. 18

(Z)-1-([1,1'-biphenyl]-4-yl)-5-phenylpent-4-en-1-one (3ag) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 70:1, v/v) to give the product as a mixture of Z/E-isomers as a white solid (53.1 mg, 85%), Selectivity (Z/E) = 79:21. 1 H NMR (500 MHz, CDCl 3 ) δ = 8.03 (d, J = 8.2 Hz, 2H), 7.68 (d, J = 8.3 Hz, 2H), 7.63 (d, J = 7.3 Hz, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.41 (d, J = 7.1 Hz, 1H), 7.38 7.29 (m, 4H), 7.25 7.19 (m, 1H), 6.50 (d, J = 11.5 Hz, 1H), 5.74 (dt, J = 11.6, 7.3 Hz, 1H), 3.15 (t, J = 7.4 Hz, 2H), 2.82 (q, J = 7.3 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ =198.9, 145.7, 139.9, 137.3, 135.6, 130.9, 123.0, 128.9, 128.7, 128.6, 128.2, 128.2, 127.2, 126.7, 126.0, 38.7, 23.3. HRMS (EI, m/z) calcd for [C 23 H 20 O]: 312.1510; found: 312.1514. (Z)-1-(4-fluorophenyl)-5-phenylpent-4-en-1-one (3ah) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 60:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (41.6 mg, 82%), Selectivity (Z/E) = 97:3. 1 H NMR (500 MHz, CDCl 3 ) δ = 8.04 7.93 (m, 2H), 7.34 (t, J = 7.4 Hz, 2H), 7.30 (d, J = 6.8 Hz, 2H), 7.23 (t, J = 7.2 Hz, 1H), 7.12 (t, J = 8.7 Hz, 2H), 6.49 (d, J = 11.6 Hz, 1H), 5.71 (dt, J = 11.6, 7.3 Hz, 1H), 3.08 (t, J = 7.5 Hz, 2H), δ 2.78 (qd, J = 7.4, 1.7 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ = 197.7, 165.7 (d, J C-F = 252.5 Hz), 137.2, 130.7 (d, J C-F = 5.0 Hz), 130.6, 130.1, 128.7, 128.2, 126.7, 126.0, 115.7 (d, J C-F = 21.3 Hz), 38.5, 23.2. HRMS (ESI, m/z) calcd for [C 17 H 15 FO+H + ]: 255.1180; found: 255.1185. 19

(Z)-5-phenyl-1-(4-vinylphenyl)pent-4-en-1-one (3ai) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a white snowflake solid (38.8 mg, 74%), Selectivity (Z/E) >99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.92 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.3 Hz, 2H), 7.33 (dt, J = 13.5, 7.3 Hz, 4H), 7.23 (t, J = 7.0 Hz, 1H), 6.75 (dd, J = 17.6, 10.9 Hz, 1H), 6.49 (d, J = 11.6 Hz, 1H), 5.88 (d, J = 17.6 Hz, 1H), 5.72 (dt, J = 11.6, 7.3 Hz, 1H), 5.40 (d, J = 10.9 Hz, 1H), 3.10 (t, J = 7.5 Hz, 2H), 2.79 (qd, J = 7.4, 1.7 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ = 198.7, 142.0, 137.3, 135.9, 130.9, 129.9, 128.7, 128.4, 128.2, 127.0, 126.7, 126.3, 116.7, 38.6, 23.3. HRMS (ESI, m/z) calcd for [C 19 H 19 O+H + ]: 263.1430; found: 263.1436. (1E,6Z)-1,7-diphenylhepta-1,6-dien-3-one (3aj) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (36.1 mg, 69%), Selectivity (Z/E) >99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.56 7.50 (m, 3H), 7.41 7.38 (m, 3H), 7.34 (t, J = 7.0 Hz, 2H), 7.30 (d, J = 6.9 Hz, 2H), 7.23 (t, J = 7.1 Hz, 1H), 6.74 (d, J = 16.2 Hz, 1H), 6.48 (d, J = 11.6 Hz, 1H), 5.69 (dt, J = 11.6, 7.1 Hz, 1H), 2.81 (d, J = 7.4 Hz, 2H), 2.74 (qd, J = 7.4, 1.7 Hz, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ = 199.4, 142.6, 137.2, 134.4, 130.8, 130.5, 129.9, 128.9, 128.7, 128.3, 128.2, 126.7, 126.0, 40.8, 23.2. HRMS (EI, m/z) calcd for [C 19 H 18 O]: 262.1351; found: 262.1358. 20

(Z)-ethyl 4-(5-phenylpent-4-enoyl)benzoate (3ak) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 45:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (59.7 mg, 97%), Selectivity (Z/E) >99:1. 1 H NMR (500 MHz, CDCl 3 ) δ = 8.11 (d, J = 8.5 Hz, 2H), 7.99 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 7.5 Hz, 2H), 7.30 (d, J = 6.9 Hz, 2H), 7.23 (t, J = 7.2 Hz, 1H), 6.49 (d, J = 11.6 Hz, 1H), 5.71 (dt, J = 11.6, 7.3 Hz, 1H), 4.41 (q, J = 7.1 Hz, 2H), 3.14 (t, J = 7.5 Hz, 2H), 2.79 (qd, J = 7.4, 1.7 Hz, 2H), 1.41 (t, J = 7.1 Hz, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 198.8, 165.7, 139.8, 137.1, 134.2, 130.5, 130.1, 129.8, 128.7, 128.2, 127.9, 126.7, 61.4, 39.0, 23.0, 14.3. HRMS (EI, m/z) calcd for [C 20 H 20 O 3 ]: 308.1414; found: 308.1412. (Z)-5-(p-tolyl)-1-(4-(trifluoromethyl)phenyl)pent-4-en-1-one (3bl) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 60:1, v/v) to give the product as a mixture of Z/E-isomers as a white solid (50.2 mg, 79%), Selectivity (Z/E) = 97:3. 1 H NMR (500 MHz, CDCl 3 ) δ = 8.04 (d, J = 8.1 Hz, 2H), 7.72 (d, J = 8.3 Hz, 2H), 7.19 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.1 Hz, 2H), 6.46 (d, J = 11.5 Hz, 1H), 5.65 (dt, J = 11.6, 7.3 Hz, 1H), 3.12 (t, J = 7.4 Hz, 2H), 2.79 (qd, J = 7.4, 1.7 Hz, 2H), 2.35 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 198.4, 139.4, 136.5, 134.5, 134.3, 130.2, 129.7, 128.9, 128.6, 128.3, 125.7 (q, J C-F = 3.8 Hz), 122.5, 39.0, 23.1, 21.1. HRMS (ESI, m/z) calcd for [C 19 H 17 F 3 O+H + ]: 319.1304; found: 319.1310. 21

(Z)-3-(5-(p-tolyl)pent-4-enoyl)benzaldehyde (3bm) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 60:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (46.1 mg, 83%), Selectivity (Z/E) = 98:2. 1 H NMR (500 MHz, CDCl 3 ) δ =10.08 (s, 1H), 8.42 (t, J = 1.6 Hz, 1H), 8.12 (dt, J = 8.0, 1.5 Hz, 1H), 8.07 (dt, J = 7.6, 1.4 Hz, 1H), 7.64 (t, J = 7.7 Hz, 1H), 7.19 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.46 (d, J = 11.6 Hz, 1H), 5.66 (dt, J = 11.6, 7.3 Hz, 1H), 3.15 (m, J = 7.5 Hz, 2H), 2.80 (qd, J = 7.4, 1.7 Hz, 2H), 2.34 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ =198.2, 191.4, 137.5, 136.6, 136.5, 134.3, 133.5, 133.4, 130.1, 129.7, 129.5, 129.2, 128.9, 128.6, 38.8, 23.1, 21.1. HRMS (ESI, m/z) calcd for [C 19 H 18 O 2 +H + ]: 279.1379; found: 279.1385. (Z)-1-(phenanthren-9-yl)-5-phenylpent-4-en-1-one (3an) The reaction was performed following the general procedure with 2 eq 2 for 24h. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a pale yellow oil (45.1 mg, 67%), Selectivity (Z/E) = 80:20. 1 H NMR (500 MHz, CDCl 3 ) 8.72 (d, J = 7.8 Hz, 1H), 8.67 (d, J = 8.3 Hz, 1H), 8.55 (d, J = 8.2 Hz, 1H), 8.10 (d, J = 18.5 Hz, 1H), 7.92 (d, J = 9.0 Hz, 1H), 7.76 7.62 (m, 4H), 7.37 7.29 (m, 4H), 7.25-7.23 (m, 1H), 6.52 (d, J = 11.5 Hz, 1H), 5.79 (dt, J = 11.6, 7.3 Hz, 1H), 3.28 (t, J = 7.4 Hz, 2H), 2.90 (qd, J = 7.4, 1.6 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ = 203.8, 137.2, 131.7, 130.8, 130.7, 130.1, 130.0, 129.6, 129.1, 128.7, 128.5, 128.3, 128.2, 127.5, 127.1, 127.1, 126.7, 126.5, 126.0, 122.8, 122.7, 42.2, 23.7. HRMS (ESI, m/z) calcd for [C 25 H 20 O 2 +H + ]: 337.1587; found: 337.1592. 22

(Z)-1-(dibenzo[b,d]furan-4-yl)-5-phenylpent-4-en-1-one (3ao) The reaction was performed following the general procedure with 24h. The residue was purified by flash column chromatograph (petroleum ether:acoet = 100:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (50.8 mg, 78%), Selectivity (Z/E) =78:22. 1 H NMR (500 MHz, CDCl 3 ) δ = 8.13 (dd, J = 7.5, 1.3 Hz, 1H), 8.07 (dd, J = 7.7, 1.3 Hz, 1H), 7.99 7.95 (m, 1H), 7.64 (d, J = 8.3 Hz, 1H), 7.53 7.50 (m, 1H), 7.48 7.44 (m, 1H), 7.43 7.38 (m, 2H), 7.36 7.29 (m, 4H), 7.24 7.21 (m, 1H), 6.53 (d, J = 11.5 Hz, 1H), 5.84 (dt, J = 11.6, 7.3 Hz, 1H), 3.51 (t, J = 7.5, 2H), 2.90 (qd, J = 7.3, 1.8 Hz, 2H). 13 C NMR (1256 MHz, CDCl 3 ) δ = 197.6, 156.1, 154.5, 137.4, 131.3, 129.8, 128.8, 128.2, 127.8, 127.7, 127.1, 126.6, 126.0, 125.8, 125.3, 123.4, 122.8, 120.7, 111.9, 43.1, 23.2. HRMS (ESI, m/z) calcd for [C 23 H 18 O 2 +H + ]: 327.1380; found: 327.1385. (Z)-1-(1H-indol-4-yl)-5-phenylpent-4-en-1-one (3ap) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 10:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (46.8 mg, 85%), Selectivity (Z/E) = 94:6. 1 H NMR (500 MHz, CDCl 3 ) δ = 8.56 (s, 1H), 8.34 (s, 1H), 7.89 (dd, J = 8.6, 1.6 Hz, 1H), 7.41 (d, J = 8.5 Hz, 1H), 7.37 7.30 (m, 4H), 7.29 7.26 (m, 1H), 7.24 7.20 (m, 1H), 6.67 (t, J = 7.5 Hz, 1H), 6.49 (d, J = 11.7, 1H), 5.77 (dt, J = 11.6, 7.3 Hz, 1H), 3.21 (t, J = 7.5 Hz, 2H), 2.83 (qd, J = 7.5, 1.7 Hz, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.6, 138.4, 137.4, 131.4, 129.7, 128.7, 128.2, 127.4, 126.6, 125.7, 122.6 122.1, 111.0, 104.3, 38.5, 23.8. HRMS (ESI, m/z) calcd for [C 19 H 17 NO+H + ]: 276.1383; found: 276.1388. 23

(8R,9S,13S,14S)-13-methyl-3-((E)-5-phenylpent-4-enoyl)-7,8,9,11,12,1 3,15,16-octahydro-6H-cyclopenta[a]phenanthren-17(14H)-one (3aq) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether:acoet = 10:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (42.6 mg, 53%), Selectivity (Z/E) = 27:73. 1 H NMR (500 MHz, CDCl 3 ) δ = 7.76 7.72 (m, 2H), 7.41 (d, J = 8.5 Hz, 1H), 7.39 7.33 (m, 2H), 7.31 (t, J = 7.7 Hz, 2H), 7.22 (t, J = 7.2 Hz, 1H), 6.49 (d, J = 15.8 Hz, 1H), 6.32 (dt, J = 15.8, 6.9 Hz, 1H), 3.15 (t, J = 7.4 Hz, 2H), 3.01 2.96 (m, 2H), 2.67 (qd, J = 7.5, 1.7 Hz, 1H), 2.57 2.46 (m, 2H), 2.22 2.15 (m, 1H), 2.12 2.07 (m, 2H), 2.01 (dd, J = 12.3, 3.0 Hz, 1H), 1.70 1.62 (m, 4H), 1.58 1.46 (m, 4H), 0.95 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.2, 145.4, 137.5, 136.9, 134.6, 130.7, 129.2, 128.7, 128.7, 128.2, 127.0, 126.0, 125.6, 125.5, 47.9, 44.7, 38.2, 37.8, 35.8, 31.5, 29.3, 27.6, 26.3, 25.6, 21.6, 13.8. The synthesis of estrone boronic acid 2q was followed by three steps as show Scheme S1. This method was according to the previous literature. 2 Scheme S1. (a) estrone 2q' (1eq), Tf 2 O (1.1 equiv), ipr 2 NEt (1 equiv), DCM, RT, 2h; (b) estrone trifluoromethanesulfonic ester (1 equiv), Pd(dppf)Cl 2 (4 mol%), bis(pinacolato)diboron (2 equiv), KOAc (3 equiv), 2 Feng, Z.; Min, Q.; Xiao, Y.; Zhang, B.; Zhang, X. Angew. Chem., Int. Ed., 2014, 53, 1669. 24

N 2, 120 o C, overnight; (c) arylborate 2q'' (1 equiv), NH 4 OAc (6 equiv), NaIO 4 (6 equiv), acetone: H 2 O (2.5:1, V/V), RT, 48 h. (4Z,6Z)-7,11-dimethyl-1-phenyldodeca-4,6,10-trien-1-one (3ma) The reaction was performed following the general procedure. The residue was purified by flash column chromatograph (petroleum ether: AcOEt = 10:1, v/v) to give the product as a mixture of Z/E-isomers as a yellow oil (46.2 mg, 82%), Selectivity (Z/E) >99:1. 1 H NMR (500 MHz, CDCl 3 ) δ =7.99 (d, J = 7.3 Hz, 2H), 7.58 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.8 Hz, 2H), 6.26 (t, J = 9.5 Hz, 1H), 6.13 (d, J = 10.5 Hz, 1H), 5.42 (ddt, J = 14.9, 10.9, 7.6 Hz, 1H), 5.17 5.09 (m, 1H), 3.09 (td, J = 7.6, 2.8 Hz, 2H), 2.64 (dd, J = 15.8, 8.3 Hz, 2H), 2.21 2.07 (m, 4H), 1.80 (d, J = 26.4 Hz, 3H), 1.70 (s, 3H), 1.63 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 199.7, 133.0, 128.7, 128.6, 128.1, 127.6, 127.2, 125.8, 124.0, 120.4, 119.6, 40.3, 32.3, 26.7, 25.6, 24.2, 22.4, 17.7. HRMS (EI, m/z) calcd for [C 20 H 26 O]: 282.1983; found: 282.1984. (Z)-2-phenyl-3-(3-(p-tolyl)allyl)-1H-indole (4) To a solution of phenylhydrazine (0.2 mmol) in anhydrous toluene was added 3ba ( 0.2 mmol) to a Schlenk tube and the resulting mixture was stirred at room temperature for 20 min. p-tsa (0.3 mmol) was then added and the mixture was heated at 80 o C for another 4 h. Upon completion of the reaction, the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatograph (silica gel, petroleum ether:acoet = 30:1, v/v) to give the desired indole as yellow oil (58.8 mg, 91%, Z/E >99:1). 1 H NMR (500 MHz, CDCl 3 ) δ = 8.04 (s, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.47 (dd, J = 8.0, 1.3 Hz, 2H), 7.39 7.31 (m, 6H), 7.24 7.19 (m, 3H), 7.13 (t, J = 7.1 Hz, 1H), 6.52 (d, J = 11.5 25

Hz, 1H), 5.90 (dt, J = 11.5, 6.9 Hz, 1H), 3.95 (dd, J = 6.8, 2.1 Hz, 2H), 2.40 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 136.3, 135.9, 134.6, 134.3, 132.8, 131.2, 128.9, 128.8, 128.7, 127.9, 127.5, 122.4, 119.6, 119.3, 112.3, 110.8, 24.4, 21.2. HRMS (EI, m/z) calcd for [C 24 H 21 N]: 323.1680; found: 323.1674. (Z)-1-phenyl-5-(p-tolyl)pent-4-en-1-ol (6) To a solution of (Z)-1-phenyl-5-(p-tolyl)pent-4-en-1-one (75 mg, 0.30 mmol) in MeOH (2 ml), NaBH 4 (27 mg, 0.6 mmol, 2 equiv) was added at 0 o C. Then, The resulting mixture was stirred at room temperature for 2 h. Upon completion of the reaction, the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatograph (silica gel, petroleum ether:acoet = 10:1, v/v) to give the desired unsaturated alcohol as yellow oil (71mg, 94%, Z/E >99:1). 1 H NMR (500 MHz, CDCl 3 ) δ = 7.36 7.30 (m, 4H), 7.30 7.26 (m, 1H), 7.21 (t, J = 7.6 Hz, 1H), 7.10 7.02 (m, 3H), 6.43 (d, J = 11.6 Hz, 1H), 5.67 (dt, J = 11.6, 7.4 Hz, 1H), 4.71 (t, J = 6.0 Hz, 1H), 2.49 2.39 (m, 2H), 2.34 (s, 3H), 2.01 1.89 (m, 2H). 13 C NMR (125MHz, CDCl 3 ) δ = 144.5, 137.7, 137.4, 131.7, 129.6, 128.4, 128.0, 127.5, 125.8, 125.7, 74.0, 39.1, 25.0, 21.4. HRMS (EI, m/z) calcd for [C 18 H 20 O]: 252.1518; found: 252.1514. (1E,4Z)-1-phenyl-5-(p-tolyl)pent-4-en-1-one oxime (9) To a solution of sodium acetate (37.5 mg, 0.45 mmol, 1.2 equiv) and hydroxylamine hydrochloride (31.5 mg, 0.45 mmol, 1.2 equiv), 3ba (75 mg, 0.30 mmol) and MeOH (2 ml) were added to the Schlenk tube under N 2. Then, the mixture was stirred at at 80 o C for 3 h. Upon completion of the reaction, the solvent was evaporated under reduced pressure and the residue was purified by flash column chromatograph (silica gel, petroleum 26

ether:acoet = 10:1, v/v) to give the desired oxime as yellow oil (Z/E >99:1). 1 H NMR (500 MHz, CDCl 3 ) δ = 9.20 (br s, 1H), 7.66 7.61 (m, 2H), 7.45 7.38 (m, 3H), 7.22 (t, J = 7.6 Hz, 1H), 7.14 7.08 (m, 2H), 7.06 (d, J = 7.5 Hz, 1H), 6.47 (d, J = 11.6 Hz, 1H), 5.74 (dt, J = 11.6, 7.4 Hz, 1H), 3.01 (t, J = 8.0, 7.4 Hz, 2H), 2.66 (dd, J = 15.9, 7.5 Hz, 2H), 2.34 (s, 3H). 13 C NMR (125 MHz, CDCl 3 ) δ = 159.0, 137.7, 135.5, 130.9, 130.0, 129.4, 128.6, 128.0, 127.4, 126.3, 125.8, 26.5, 25.4, 21.4. HRMS (EI, m/z) calcd for [C 18 H 29 NO]: 265.1469; found: 265.1467. 27

9. NMR spectroscopic data (E)-2-benzylidenecyclobutanone (1a) 28

(Z)-1,5-diphenylpent-4-en-1-one (3aa) 29

(Z)-1-phenyl-5-(p-tolyl)pent-4-en-1-one (3ba) 30

(Z)-1-phenyl-5-(m-tolyl)pent-4-en-1-one (3ca) 31

(Z)-1-phenyl-5-(o-tolyl)pent-4-en-1-one (3da) 32

(Z)-5-(4-methoxyphenyl)-1-phenylpent-4-en-1-one (3ea) 33

(Z)-5-(4-fluorophenyl)-1-phenylpent-4-en-1-one (3fa) 34

(Z)-5-(4-(tert-butyl)phenyl)-1-phenylpent-4-en-1-one (3ga) 35

(Z)-N-(4-(5-oxo-5-phenylpent-1-en-1-yl)phenyl)acetamide (3ha) 36

(Z)-1-phenyl-5-(thiophen-2-yl)pent-4-en-1-one (3ia) 37

(Z)-5-(4-(benzo[b]thiophen-3-yl)phenyl)-1-phenylpent-4-en-1-one (3ja) 38

(Z)-5-(furan-2-yl)-1-phenylpent-4-en-1-one (3ka) 39

(E)-5-(naphthalen-1-yl)-1-phenylpent-4-en-1-one (3la) 40

(Z)-5-phenyl-1-(p-tolyl)pent-4-en-1-one (3ab) 41

(Z)-1-(4-methoxyphenyl)-5-phenylpent-4-en-1-one (3ac) 42

(Z)-1-(4-(tert-butyl)phenyl)-5-phenylpent-4-en-1-one (3ad) 43

(Z)-5-phenyl-1-(4-propylphenyl)pent-4-en-1-one (3ae) 44

(Z)-1-(3,5-dimethylphenyl)-5-phenylpent-4-en-1-one (3af) 45

(Z)-1-([1,1'-biphenyl]-4-yl)-5-phenylpent-4-en-1-one (3ag) 46

(Z)-1-(4-fluorophenyl)-5-phenylpent-4-en-1-one (3ah) 47

(Z)-5-phenyl-1-(4-vinylphenyl)pent-4-en-1-one (3ai) 48

(1E,6Z)-1,7-diphenylhepta-1,6-dien-3-one (3aj) 49

(Z)-ethyl 4-(5-phenylpent-4-enoyl)benzoate (3ak) 50

(Z)-5-(p-tolyl)-1-(4-(trifluoromethyl)phenyl)pent-4-en-1-one (3bl) 51

(Z)-3-(5-(p-tolyl)pent-4-enoyl)benzaldehyde (3bm) 52

(Z)-1-(phenanthren-9-yl)-5-phenylpent-4-en-1-one (3an) 53

(Z)-1-(dibenzo[b,d]furan-4-yl)-5-phenylpent-4-en-1-one(3ao) 54

(Z)-1-(1H-indol-4-yl)-5-phenylpent-4-en-1-one (3ap) 55

(8R,9S,13S,14S)-13-methyl-3-((E)-5-phenylpent-4-enoyl)-7,8,9,11,12,1 3,15,16-octahydro-6H-cyclopenta[a]phenanthren-17(14H)-one (3aq) 56

(4Z,6Z)-7,11-dimethyl-1-phenyldodeca-4,6,10-trien-1-one (3ma) 57

(Z)-2-phenyl-3-(3-(p-tolyl)allyl)-1H-indole (4) 58

(Z)-1-phenyl-5-(p-tolyl)pent-4-en-1-ol (6) 59

(1E,4Z)-1-phenyl-5-(p-tolyl)pent-4-en-1-one oxime (9) 60