Supporting Information

Transcript

1 Supporting Information Wiley-VCH Weinheim, Germany

2 Ligand-Free Pd-Catalyzed Highly Selective Arylation of Allylic Esters with Retention of the Traditional Leaving Group (Supporting Information) Delin Pan, a Anjun Chen, b Yijin Su, a Wang Zhou, a Si Li, a Wei Jia, a Juan Xiao, a Qingjian Liu, b Liangren Zhang, a and Ning Jiao*,a a State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing , China b Department of Chemistry, Shandong Normal University, Jinan , China jiaoning@bjmu.edu.cn Fax: (+86) Supporting Information Table of Contents Screening with different catalysts, solvents, bases and additives Analytical data for compounds 3 S2 S4 1 H NMR and 13 C NMR spectra of those compounds S12 1

3 Table 1. The results of different Pd catalysts catalyzed reactions between bromobenzene 1b and allylic acetate 2a in different solvent. [a] PhBr + OAc Pd cat. (5 mol%) Ag 2 CO 3 (0.6 eq.) Ph OAc 1b 2a solvent E-3a enty solvent T ( o C) Pd-catalyst yield of E-3a (%) 1 benzene reflux PdCl benzene reflux Pd 2 (dba) 3 trace 3 benzene reflux Pd(O 2 CCF 3 ) benzene reflux Pd(CN) 2 Cl [b] benzene reflux Pd(PPh 3 ) DMF 120 Pd(OAc) [c] 1,4-100 Pd(OAc) 2 39 dioxane 8 [c] toluene reflux Pd(OAc) toluene reflux Pd(OAc) [c] CH 3 CN 80 Pd(OAc) [c] H 2 O 100 Pd(OAc) 2 0 [a] The reactions were carried out with bromobenzene 1b (0.6 mmol) and allylic acetate 2a (0.5 mmol) in solvent (3 ml) in the presence of Pd-catalyst (0.025 mmol) and Ag 2 CO 3 (0.3 mmol) refluxed for 24 h under air. [b] The reaction was carried out under N 2. [c] 1b (1.0 mmol) and 2a (0.5 mmol) were used. Table 2. The effect of ligands, bases and additives in the Pd(OAc) 2 catalyzed Heck reaction of bromobenzene 1b with allylic acetate 2a. [a] Pd(OAc) 2 (5 mol%) ligand (10 mol%) PhBr + OAc additives Ph OAc 1b 2a benzene, reflux, 24 h E-3a enty ligand base (eq.) additives (eq.) 1 Ag 2 CO 3 (1.0) 59 2 [b] Ag 2 CO 3 (0.4) 37 3 [b] Ag 2 CO 3 (0.2) 28 4 N H yield of E- 3a(%) Ph Ag 2 CO 3 (0.6) trace OH Ph 5 dppe Ag 2 CO 3 (0.6) 12 6 [c] PPh 3 Ag 2 CO 3 (0.6) 10 7 bipyridine Ag 2 CO 3 (0.6) 0 8 K 2 CO 3 (2.0) <5 9 K 2 CO 3 (2.0) Ag 2 CO 3 (0.6) <5 10 KOAc (2.0) trace 11 Et 3 N (2.0) <5 12 dppe Et 3 N (2.0) 0 13 AgNO 3 (1.2) 0 [a] The reactions were carried out with bromobenzene 1b (1.0 mmol) and allylic acetate 2a (0.5 mmol) in benzene (3 ml) in the presence of Pd(OAc) 2 (0.025 mmol), ligand (0.05 mmol) and Ag 2 CO 3 (0.3 mmol) refluxed for 24 h. [b] The reaction was refluxed in toluene. [c] 0.1 mmol of PPh 3 was used. 2

4 Table 3. The effect of silver salts and additives in the Pd(OAc) 2 catalyzed Heck reaction of iodobenzene 1a with allylic acetate 2a. [a] Pd(OAc) 2 (5 mol%) PhI + OAc silver salts additives Ph OAc 1a 2a benzene, reflux, 24 h under air E-3a enty Silver salts base (eq.) additives (eq.) yield of E-3a(%) (eq.) 1 Ag 2 O (0.6) 7 2 AgOAc (1.2) 55 3 Ag 2 CO 3 (0.6) H 2 O (2.0) 84 4 [b] Ag 2 CO 3 (0.6) oxone (2.0) 46 [a] The reactions were carried out with iodobenzene 1a (0.5 mmol) and allylic acetate 2a (1.0 mmol) in benzene (3 ml) in the presence of Pd(OAc) 2 (0.025 mmol), refluxed for 24 h. [b] The reaction was carried out under N 2. PhI + OAc Pd(OAc) 2 (1 mol%) Ag 2 CO 3 (0.6 eq) benzene, reflux, 48 h Ph OAc 1a 2a yield, 59 % E-3a PhBr + 1b 0.6 mmol Pd(OAc) 2 (5 mol%) OAc AgCO 3 (0.6 eq.) toluene, reflux, 48 h 2a under O 2 (1 atm) 0.5 mmol Ph E-3a Scheme 1 Ph OAc + Ph Ph Ph + 7 OAc Ph 8 OAc 54% 7% 17% 3

5 Ph OAc Experimental section: 1) E-3a (E)-3-(Phenyl)-2-propen-1-ol acetate (E-3a). [1] Typical procedure: To a mixture of Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) was added iodobenzene 1a (102 mg, 0.5 mmol) and allylic acetate 2a (100 mg, 1.0 mmol) subsequently. The resulting mixture was refluxed for 10 h monitored by TLC. After evaporation, the residue was carefully purified by flash chromatography on silica gel (eluent: petroleum ether/ether = 10:1) to afford 83 mg (94 %) of E-3a; The reaction of 1b (95 mg, 0.6 mmol), and 2a (50 mg, 0.5 mmol) refluxed in toluene (3 ml) afforded 57 mg (65%) of E-3a; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 6.66 (d, J = 15.6 Hz, 1 H), 6.29 (dt, J = 15.6, 6.3 Hz, 1 H), 4.73 (d, J = 6.3 Hz, 2 H), 2.11 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 65.05, 20.98; MS (70 ev): m/z (%): (17) [M + ], 43 (100); IR (neat): ν = 1739, 1653, 1236, 1027 cm -1. OAc E-3b 2) Me (E)-3-(4 -Methylphenyl)-2-propen-1-ol acetate (E-3b). [2] The reaction of 1c (109 mg, 0.5 mmol), 2a (100 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 93 mg (98%) of E-3b; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = 7.29 (d, J = 8.1 Hz, 2 H), 7.13 (d, J = 8.1 Hz, 2 H), 6.62 (d, J = 15.9 Hz, 1 H), 6.23 (dt, J = 15.9, 6.6 Hz, 1 H), 4.71 (dd, J = 6.6, 1.2 Hz, 2 H), 2.34 (s, 3 H), 2.09 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 65.23, 21.21, 20.02; MS (70 ev): m/z (%): (1.5) [M + ], (100); IR (neat): ν = 1739, 1513, 1233 cm -1. CH 3 OAc 3) E-3c (E)-3-(2 -Methylphenyl)-2-propen-1-ol acetate (E-3c). The reaction of 1d (107 mg, 0.5 mmol), 2a (100 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in toluene (3 ml) afforded 82 mg (80%) of E-3c; The reaction of 1k (103 mg, 0.6 mmol), and 2a (50 mg, 0.5 mmol) Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in toluene (3 ml) afforded 67 mg (71%) of E-3c; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 1 H), (m, 3 H), 6.87 (d, J = 15.7 Hz, 1 H), 6.17 (dt, J = 15.7, 6.4 Hz, 1 H), 4.74 (dd, J = 6.4, 1.2 Hz, 2 H), 2.35 (s, 3 H), 2.10(s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , , 65.29, 20.99, 19.70; MS (70 ev): m/z (%): (24.8) [M + ], (100); IR (neat): ν = 1740, 4

6 1486, 1231, 1026, 966 cm -1 ; HRMS m/z (ESI) calcd for C 12 H 14 O 2 Na (M + Na) , found ; OAc E-3d 4) MeOOC (E)-3-(4 -Methoxycarbonylphenyl)-2-propen-1-ol acetate (E-3d). The reaction of 1e (65.5 mg, 0.25 mmol), 2a (50 mg, 0.5 mmol), Pd(OAc) 2 (2.8 mg, mmol) and Ag 2 CO 3 (41 mg, 0.15 mmol) in benzene (2 ml) afforded 82 mg (80%) of E-3d; The reaction of 1l (53.5 mg, 0.25 mmol), 2a (75 mg, 0.75 mmol), Pd(OAc) 2 (2.8 mg, mmol) and Ag 2 CO 3 (41 mg, 0.15 mmol) in toluene (5 ml) afforded 36 mg (65%) of E-3d, and 4 mg (7 %) of 1l was recovered; E-3d: solid; Mp (n-hexane/ethyl acetate): ; 1 H NMR (CDCl 3, 300 MHz): δ = 8.00 (d, J = 8.25 Hz, 2 H), 7.45 (d, J = 8.25 Hz, 2 H), 6.69 (d, J = 16.1 Hz, 1 H), 6.40 (dt, J = 16.1, 6.15 Hz, 1 H), 4.76 (dd, J = 6.15, 0.8 Hz, 2 H), 3.91 (s, 3 H), 2.12 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , 64.58, 52.04, 20.87; MS (70 ev): m/z (%): (36.0) [M + ], (100); IR (neat): ν = 1743, 1721, 1608, 1440, 1291, 1232 cm -1 ; Anal calcd for C 13 H 14 O 4 (%): C 66.66, H 6.02, Found: C 66.79, H OAc E-3e 5) O 2 N (E)-3-(4 -Nitrylphenyl)-2-propen-1-ol acetate (E-3e). [3] The reaction of 1f (125 mg, 0.5 mmol), 2a (100 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 91 mg (81%) of E-3e; The reaction of 1m (101 mg, 0.5 mmol), 2a (150 mg, 1.5 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in toluene (5 ml) afforded 69 mg (62%) of E-3e, and 19 mg (19%) of 1m was recovered; E-3e: solid; 1 H NMR (CDCl 3, 300 MHz): δ = 8.20 (d, J = 8.85 Hz, 2 H), 7.53 (d, J = 8.85 Hz, 2 H), 6.72 (d, J = 15.9 Hz, 1 H), 6.46 (dt, J = 15.9, 5.85 Hz, 1 H), 4.78 (dd, J = 5.85, 1.2 Hz, 2 H), 2.14 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , 64.13, 20.76; MS (70 ev): m/z (%): (8.0) [M + ], (100); IR (neat): ν = 2450, 1929, 1740, 1597, 1516, 1343, 1258, 1227, 1026, 447 cm -1. OAc E-3f 6) F (E)-3-(4 -Fluorophenyl)-2-propen-1-ol acetate (E-3f). The reaction of 1g (111 mg, 0.5 mmol), 2a (100 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 78 mg (80%) of E-3f; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = 7.36 (dd, J = 8.7, 5.4 Hz, 2 H), 7.02 (t, J = 8.7 Hz, 2 H), 6.62 (d, J = 15.9 Hz, 1 H), 6.20 (dt, J = 15.9, 6.45 Hz, 1 H), 4.71 (dd, J = 6.45, 1.05 Hz, 2 H), 2.11 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , (d, J = Hz), , 5

7 (d, J = 3.70 Hz), (d, J = 8.15 Hz), (d, J = 2.49 Hz), (d, J = Hz), 64.87, 20.88; MS (70 ev): m/z (%): (15.3) [M + ], (100); IR (neat): ν = 1740, 1602, 1510, 1230, 1026, 967, 849 cm -1 ; HRMS m/z (ESI) calcd for C 11 H 11 F 1 O 2 Na (M + Na) , found OAc E-3g 7) Ph (E)-3-(4 -Phenylphenyl)-2-propen-1-ol acetate (E-3g). [2] The reaction of 1h (70 mg, 0.25 mmol), 2a (50 mg, 0.5 mmol), Pd(OAc) 2 (2.8 mg, mmol) and Ag 2 CO 3 (41 mg, 0.15 mmol) in benzene (3 ml) afforded 50 mg (79 %) of E-3g: solid; Mp: (n-hexane/ethyl acetate); 1 H NMR (CDCl 3, 300 MHz): δ = (m, 4 H), (m, 4 H), (m, 1 H), 6.69 (d, J = Hz, 1 H), 6.33 (dt, J = 15.75, 6.53 Hz, 1 H), 4.75 (dd, J = 6.53, 1.05 Hz, 2 H), 2.12 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , , , , 65.07, 21.00; MS (70 ev): m/z (%): (93.5) [M + ], (100); IR (neat): ν = 1736, 1488, 1384, 1362, 1252, 760 cm -1. OAc O E-3h 8) (E)-3-(4 -Acetylphenyl)-2-propen-1-ol acetate (E-3h). The reaction of 1i (58 mg, 0.25 mmol), 2a (50 mg, 0.5 mmol), Pd(OAc) 2 (2.8 mg, mmol) and Ag 2 CO 3 (41 mg, 0.15 mmol) in benzene (2 ml) afforded 45 mg (82 %) of E-3h: liquid; 1 H NMR (CDCl 3, 300 MHz): δ = 7.92 (dd, J = 8.4, 1.65 Hz, 2 H), 7.47 (d, J = 8.4 Hz, 2 H), 6.69 (d, J = 15.9 Hz, 1 H), 6.41 (dt, J = 15.9, 6.25 Hz, 1 H), 4.76 (dd, J = 6.25, 1.2 Hz, 2 H), 2.60 (d, J = 2.7 Hz, 3 H), 2.13 (d, J = 3.0 Hz, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , 64.54, 26.52, 20.87; MS (70 ev): m/z (%): (34.5) [M + ], (100); IR (neat): ν = 1740, 1681, 1603, 1361, 1267, 1232 cm -1 ; HRMS m/z (ESI) calcd for C 13 H 14 O 3 Na (M + Na) , found OAc E-3i 9) MeO (E)-3-(4 -Methoxyphenyl)-2-propen-1-ol acetate (E-3i). [4] The reaction of 1j (117 mg, 0.5 mmol), 2a (100 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in toluene (3 ml) afforded 83 mg (81%) of E-3i; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = 7.33 (d, J = 8.7 Hz, 2 H), 6.86 (d, J = 8.7 Hz, 2 H), 6.61 (d, J = 15.7 Hz, 1 H), 6.16 (dt, J = 15.7, 6.64 Hz, 1H), 4.71 (d, J = 6.64 Hz, 2 H), 3.81 (s, 3 H), 2.10 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 65.30, 55.20, 20.98; MS (70 ev): m/z (%):206.2 (97.3) [M + ], (100); IR (neat): ν = 6

8 1738, 1608, 1513, 1248, 1032 cm -1. OAc S 10) E-3j (E)-3-(2 -Thienyl)-2-propen-1-ol acetate (E-3j). [5] The reaction of 1n (105 mg, 0.5 mmol), 2a (100 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 68 mg (75%) of E-3j; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = 7.18 (d, J = 4.8 Hz, 1 H), (m, 2 H), 6.78 (d, J = 15.6 Hz, 1 H), 6.11 (dt, J = 15.6, 6.52 Hz, 1 H), 4.68 (dd, J = 6.52, 1.35 Hz, 2 H), 2.09 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , 64.69, 20.94; MS (70 ev): m/z (%): (1.0) [M + ], 43.2 (100); IR (neat): ν = 2927, 1738, 1653, 1235, 1027 cm -1. C 4 H 9 OAc 11) E-3k (2E, 4E)-2,4-Nonadienyl-1-ol acetate (E-3k). [6] The reaction of 1o (105 mg, 0.5 mmol), 2a (150 mg, 1.5 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (10 ml) afforded 50 mg (55%) of E-3k; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = 6.26 ( dd, J = 15.3, 10.5 Hz,1 H), 6.04 (dd, J = 15.3, 10.5 Hz 1 H), (m, 2 H), 4.57 (d, J = 6.6 Hz, 2 H), 2.06 (s, 3 H), (m, 2 H), (m, 4 H), 0.89 (t, J = 6.9 Hz, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , 65.00, 32.28, 31.22, 22.18, 21.01, 13.89; MS (70 ev): m/z (%): (1.1) [M + ], 81.0 (100); IR (neat): ν = 3431, 2960, 2927, 2858, 1742, 1661, 1261, 1097, 1025, 804 cm -1. Ph OAc 12) E-3l (2E, 4E)-5-Phenylpenta-2,4-dienyl-1-ol acetate (E-3l). [6] The reaction of 1p (105 mg, 0.46 mmol), 2a (150 mg, 1.5 mmol) Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (10 ml) afforded 61 mg (60%) of E-3l; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 6.77 (dd, J = 15.6, Hz, 1 H), 6.58 (d, J = 15.6 Hz, 1 H), 6.45 (dd, J = 15.45, Hz, 1 H), 5.87 (dt, J = 15.45, 6.4 Hz, 1 H), 4.65 (d, J = 6.4 Hz, 2 H), 2.09 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , , 64.73, 20.96; MS (70 ev): m/z (%): (42.5) [M + ], (100); IR (neat): ν = 1741, 1678, 1450, 1366, 1236, 991, 750, 694 cm -1. Ph OAc 13) E-3m (E)-4-Phenyl-3-buten-2-ol acetate (E-3m). [7] The reaction of 1a (102 mg, 0.5 mmol), 2b (114 mg, 1.0 7

9 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 43 mg (45%) of E-3m; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 6.52 (d, J = Hz, 1 H), 6.11 (dd, J = 15.98, 6.75 Hz, 1 H), (m, 1 H), 1.99 (s, 3 H), 1.33 (d, J = 6.6 Hz, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 70.95, 21.36, 20.33; MS (70 ev): m/z (%): (13.5) [M + ], 43.1 (100); IR (neat): ν = 2981, 1737, 1372, 1242, 1042, 749 cm -1. Et Ph OAc 14) E-3n (E)-1-Phenyl-1-penten-3-ol acetate (E-3n). [8] The reaction of 1a (102 mg, 0.5 mmol), 2c (128 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 89 mg (87%) of E-3n; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 6.53 (d, J = Hz, 1 H), 6.05 (dd, J = 16.05, 7.05 Hz, 1 H), 5.27 (q, J = 6.8 Hz, 1 H), 2.01 (s, 3 H), (m, 2 H), 0.87 (t, J = 7.35 Hz, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 75.90, 27.51, 21.22, 9.49; MS (70 ev): m/z (%): (12.2) [M + ], 43.1 (100); IR (neat): ν = 2969, 1738, 1452, 1371, 1240, 1021, 965, 749 cm -1. Ph OAc 15) E-3o (E)-4-Methyl-1-phenyl-1-penten-3-ol acetate (E-3o). [9] The reaction of 1a (102 mg, 0.5 mmol), 2d (142 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 107 mg (98%) of E-3o; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 6.51 (d, J = 15.9 Hz, 1 H), 6.03 (dd, J = 15.9, 7.3 Hz, 1 H), 5.12 (t, 7.3 Hz, 1 H), 1.99 (s, 3 H), (m, 1 H), 0.88 (d, J = 6.6 Hz, 3 H), 0.86 (d, J = 6.6 Hz, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 79.29, 32.21, 21.16, 18.15, 18.06; MS (70 ev): m/z (%): (5.5) [M + ], (100); IR (neat): ν = 2965, 1737, 1240, 1019, 970 cm -1. Ph Ph OAc 16) E-3p (E)-1,3-Diphenyl-2-propen-1-ol acetate (E-3p). [10] The reaction of 1a (212 mg, 2.0 mmol), 2e (378 mg, 2.10 mmol), Pd(OAc) 2 (22.4 mg, 0.1 mmol) and Ag 2 CO 3 (332 mg, 1.2 mmol) in toluene (10 ml) afforded 370 mg (73%) of E-3p; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 10 H), 6.55 (d, J =

10 Hz, 1 H), 6.36 (d, J = 6.9 Hz, 1 H), 6.26 (dd, J = 15.6, 6.9 Hz, 1 H), 2.05 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , , 76.09, 21.30; MS (70 ev): m/z (%): (17.8) [M + ], (100); IR (neat): ν = 1739, 1494, 1370, 1232, 1019, 965, 747, 698 cm -1. Ph OAc 17) E-3q (E)-3-Phenyl-2-methyl-2-propen-1-ol acetate (E-3q). [11] The reaction of 1a (102 mg, 0.5 mmol), 2f (114 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 69 mg (73%) of 3q (E-3q/Z-3q = 80:20), they were difficult to separate and purify; E-3q: liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 6.53 (s, 1 H), 4.64 (s, 2 H), 2.13 (s, 3 H), 1.90 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 70.13, 21.00, 15.52; MS (70 ev): m/z (%): (7.8) [M + ], 91.1 (100); IR (neat): ν = 1740, 1493, 1231, 1024, 700 cm -1. Ph O 2 N OAc 18) Z-3r (E)-3-(4 -Nitrylphenyl)-2-phenyl-2-propen-1-ol acetate (Z-3r). The reaction of 1f (124 mg, 0.5 mmol), 2g (180 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 138 mg (92%) of 3r (Z-3r/E-3r = 81:19), they were difficult to separate and purify; Z-3r: solid; Mp: (n-hexane/ethyl acetate); 1 H NMR (CDCl 3, 300 MHz): δ = 8.26 (d, J = 8.7 Hz, 2 H), (m, 4 H), (m, 3 H), 7.09 (s, 1 H), 5.11 (s, 2 H), 2.03 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , , , 61.42, 20.86; MS (70 ev): m/z (%):297.1 (16.5) [M + ], (100); IR (neat): ν = 1722, 1593, 1514, 1342, 1249, 759 cm -1 ; HRMS m/z (ESI) calcd for C 17 H 15 NO 4 Na (M + Na) , found O 2 N Ph OAc E-3r (Z)-3-(4 -Nitrylphenyl)-2-phenyl-2-propen-1-ol acetate (E-3r). 1 H NMR (CDCl 3, 300 MHz): δ = 7.97 (d, J = 8.6 Hz, 2 H), (m, 3 H), (m, 2 H), 7.11 (d, J = 8.6 Hz, 2 H), 6.72 (s, 1 H), 4.94 (s, 2 H), 2.10 (s, 3 H). 9

11 O 2 N OAc Ph 19) E-3s (E)-3-(4 -Nitrylphenyl)-1-phenyl-2-propen-1-ol acetate (E-3s). The reaction of 1f (124 mg, 0.5 mmol), 2e (180 mg, 1.0 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 130 mg (87%) of E-3s: solid; Mp: (n-hexane/ethyl acetate); 1 H NMR (CDCl 3, 300 MHz): δ = 8.17 (d, J = 8.8 Hz, 2 H), 7.51 (d, J = 8.8 Hz, 2 H), (m, 5 H), 6.69 (d, J = 15.3 Hz, 1 H), 6.55 (d, J = 6.3 H, 1 H), 6.47 (dd, J = 15.3, 6.3 Hz, 1 H), 2.16 (s, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , , , , , 75.48, 21.18; MS (70 ev): m/z (%): (2.1) [M + ], (100); IR (neat): ν = 1739, 1598, 1513, 1343, 1238 cm -1 ; Anal calcd for C 17 H 15 NO 4 (%): C 68.68, H 5.09, N 4.71, Found: C 68.17, H 5.05, N Ph Ph & OAc OAc 20) 3t 4 2-Cyclohexylidene-2-phenyl-ethanol acetate (3t) and 2-(1 -Cyclohexenyl)-2- phenyl-ethanol acetate (4). The reaction of 1a (102 mg, 0.5 mmol), 2h (252 mg, 1.5 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (10 ml) afforded 79 mg (65%) of 3t and 4 (3t/4 = 12:88), they were difficult to separate and purify; 4: liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 5.59 (brs, 1 H), 4.47 (dd, J = 11.0, 7.5 Hz, 1H), 4.33 (dd, J = 11.0, 7.5 Hz, 1 H), 3.50 (t, J = 7.5 Hz, 1 H), (m, 4 H), 1.98 (s, 3 H), (m, 4 H); MS (70 ev): m/z (%): (2.0) [M+1] +, 91.0 (100); IR (neat): ν = 2928, 1740, 1369, 1241, 1032, 702 cm -1. HRMS m/z (ESI) calcd for C 16 H 20 O 2 Na (M + Na) , found O O OMe 21) E-6 (E)-3-(Phenyl)-2-propen-1-ol mythyl carbonate (E-6). [2] The reaction of 1a (102 mg, 0.5 mmol), 5 (150 mg, 1.3 mmol), Pd(OAc) 2 (5.6 mg, mmol) and Ag 2 CO 3 (83 mg, 0.3 mmol) in benzene (3 ml) afforded 90 mg (94%) of E-6; liquid; 1 H NMR (CDCl 3, 300 MHz): δ = (m, 5 H), 6.69 (d, J = 15.7 Hz, 1 H), 6.31 (dt, J = 15.7, 6.3 Hz, 1 H), 4.79 (dd, J = 6.3, 1.2 Hz, 2 H), 3.80 (d, J = 1.2 Hz, 3 H); 13 C NMR (CDCl 3, 75.4 MHz): δ = , , , , , , , 68.36, 54.79; MS (70 ev): m/z (%): (28.1) [M + ], (100); IR (neat): ν = 1749, 1446, 1267, 968, 949 cm -1 10

12 References [1] I. S. Kim, G. R. Dong, Y. H. Jung, J. Org. Chem. 2007, 72, [2] J. Lehmann, G. C. Lloyd-Jones, Tetrahedron. 1995, 51, [3] K. Atsushi, T. Shigemitsu, Y. Kazumi, A. Hitoshi, H. Takashi, Chem. Pharm. Bull. 2002, 50, [4] M. Al-Masum, Y. Yamamoto, J. Am. Chem. Soc. 1998, 120, [5] M. Iwasaki, Y. Kobayashi, J-P. Li, H. Matsuzaka, Y. Ishii, M. Hidai, J. Org. Chem. 1991, 56, [6] Y. Ishii, C. Gao, W-X. Xu, M. Iwasaki, M. Hidai, J. Org. Chem. 1993, 58, [7] M. B. Onaran, C. T. Seto, J. Org. Chem. 2003, 68, [8] U. Kazmaier, F. L. Zumpe, Eur. J. Org. Chem. 2001, [9] R. S. Atkinson, S. Ulukanli, P. J. Williams, J. Chem. Soc., Perkin Trans. 1, 1999, [10] I. D. G. Watson, A. K. Yudin, J. Am. Chem. Soc. 2005, 127, [11] M. Takashi, H. Masao, K. Tsuyoshi, J. Chem. Soc., Perkin Trans. 2, 1985,

13 12

14 13

15 14

16 15

17 16

18 17

19 18

20 19

21 20

22 21

23 22

24 23

25 24

26 25

27 26

28 27

29 28

30 29

31 30

32 31

33 32

34 33

35 34

36 35

37 36

38 37

39 38

40 39

41 40

42 41

43 42

44 43

45 44

46 45

47 46

48 47

49 48

50 49

51 50

52 51

53 52

54 53

55 54

56 55