Kishore Natte, Jianbin Chen, Helfried Neumann, Matthias Beller, and Xiao-Feng Wu*

Transcript

1 Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 204 Kishore Natte, Jianbin Chen, Helfried Neumann, Matthias Beller, and Xiao-Feng Wu* Leibniz-Institut für Katalyse an der Universität Rostock, Albert-Einstein-Straße 29a, 8059 Rostock (Germany) General Methods NMR spectra were recorded on Bruker Avance 300 and Bruker ARX 400 spectrometers. Multiplets were assigned as s (singlet), d (doublet), t (triplet), dd (doublet of doublet), m (multiplet) and br. s (broad singlet). All measurements were carried out at room temperature unless otherwise stated. Electron impact (EI) mass spectra were recorded on AMD 402 mass spectrometer (70 ev). High resolution mass spectra (HRMS) were recorded on Agilent 620. The data are given as mass units per charge (m/z). Gas chromatography analysis was performed on an Agilent HP-5890 instrument with a FID detector and HP-5 capillary column (polydimethylsiloxane with 5% phenyl groups, 30 m, 0.32 mm i.d., 0.25 μm film thickness) using argon as carrier gas. The products were isolated from the reaction mixture by column chromatography on silica gel 60, mm, mesh (Merck). General Procedure: The reaction was carried out in a Parr Instruments 4560 series 300 ml autoclave containing an alloy plate with wells for six 4 ml Wheaton vials. Pd(TFA) 2 (5.0 mol%), DPPP (0.0 mol%), Ag 2 (2 equiv.), phenylboronic acid (0.5 mmol), NaAc (2 equiv.) and a magnetic stir bar were placed in each vials under air, which were then capped with a septum equipped with an inlet needle. Then -hexyne (.2 equiv.) and acetone ( ml) were added to the vial via syringe. The vials were placed in an autoclave, filled with 8 bar of C at room temperature and keep the reaction at room temperature for 2 h. After the reaction was completed, the autoclave was vented to discharge N 2. The product was extracted with ethyl acetate (5 3 ml). The organic layers were washed with brine, dried over Na 2 S 4, and evaporated to yield the crude reaction mixture. The purification occurred by flash chromatography on silica gel (eluent: heptane/etac 95:05).

2 -Phenylhept-2-yn--one H NMR (300 MHz, Chloroform-d) δ (m, 2H), (m, 2H), 7.49 (m, H), 2.5 (t, 2H),.75.6 (m, 2H), (m, 2H), 0.98 (t, J = 7.3 Hz, 3H). C NMR (75 MHz, Chloroform-d) δ 78.39, 7.06, 3.99, 29.67, 28.6, 96.99, 79.80, 29.98, 22.22, 9.06,.67. MS (EI, 70 ev): m/z (%) = 86 ([M] +, 20), 7 (0), 57 (40), 44 (00), 29 (30), 5 (60), 05 (62), 77 (50), 66 (0), 5 (2). F 3 C -(4-(Trifluoromethyl)phenyl)hept-2-yn--one H NMR (300 MHz, Chloroform-d) δ (m, 3H), (m, 2H), 2.46 (t, J = 7. Hz, 2H), (m, 2H),.5.36 (m, 2H), 0.90 (t, J = 7.3 Hz, 3H). C NMR (75 MHz, Chloroform-d) δ 76.94, 9.45, 5.0 (q, J = 32.5 Hz), 29.8, (q, J = 3.86 Hz), (q, J = Hz), 98.45, 79.48, 29.78, 22.2, 8.98,.53. MS (EI, 70 ev): m/z (%) = 254 ([M] +, 5), 235 (0), 225 (20), 22 (00), 73 (90), 85 (20), 73 (90), 45 (50), 09 (5), 79 (0). Cl -(4-Chlorophenyl)hept-2-yn--one H NMR (400 MHz, Chloroform-d) δ (m, 2H), (m, 2H), 2.43 (t, J = 7. Hz, 2H),.66.5 (m, 2H), (m, 2H), 0.89 (t, J = 7.3 Hz, 3H). C NMR (0 MHz, Chloroform-d) δ 76.90, 40.46, 5.37, 0.87, 28.87, 97.46, 79.42, 29.83, 22.2, 8.96,.54. MS (EI, 70 ev): = 220 ([M] +, 0), 9 (5), 78 (00), 57 (0), 9 (90), 28 (7), (40), 79 (20).

3 -(3,5-Dimethylphenyl)hept-2-yn--one H NMR (400 MHz, Chloroform-d) δ 7.67 (s, 2H), (m, H), 2.43 (t, J = 7. Hz, 2H), 2.30 (s, 6H),.66.5 (m, 2H), (m, 2H), 0.90 (t, J = 7.3 Hz, 3H). C NMR (0 MHz, Chloroform-d) δ 78.2, 8.9, 5.64, 2.8, 27.37, 97.46, 79.93, 29.89, 23.02, 22., 2.44, MS (EI, 70 ev): = 24 ([M] +, 96), 99 (70), 72 (00), 57 (30), 43 (85), 3 (80), 5 (20), 05 (5), 9 (0), 79 (40), 66 (5), 53 (8). S -(4-(Methylthio)phenyl)hept-2-yn--one H NMR (300 MHz, Chloroform-d) δ (m, 2H), (m, 2H), 2.5 (s, 3H), (m, 2H), (m, 2H), (m, 2H), 0.89 (t, J = 7.2 Hz, 3H). C NMR (0 MHz, Chloroform-d) δ 77.25, 47.8, 3.50, 29.87, 24.72, 96.44, 79.60, 29.87, 22.09, 8.92, 4.73, 4.70,.54. MS (EI, 70 ev): = 232 ([M] +, 00), 203 (5), 90 (0), 75 (8), 6 (0), 5 (2). -(Naphthalen-2-yl)hept-2-yn--one H NMR (300 MHz, Chloroform-d) δ (s, H), 8.07 (dd, J = 8.7,.7 Hz, 2H), (m, 2H), 7.8 (dd, J = 8.,.7 Hz, 2H), 2.49 (t, J = 7.0 Hz, 2H), (m, 2H), (m, 2H), 0.93 (t, J = 7.3 Hz, 3H). C NMR (0 MHz, Chloroform-d) δ78.9, 6.06, 4.49, 2.62, 2.4, 29.8, 28.86, 28.38, 27.89, 26.85, 24.02, 96.79, 79.84, 29.90, 22.4, 9.0,.57. MS (EI, 70 ev): = 236 ([M] +, 00 ), 207 (20), 94 (8), 79 (0), 65 (50), 55 (5).

4 F -(3-Fluorophenyl)hept-2-yn--one H NMR (300 MHz, Chloroform-d) δ 7.86 (dt, J = 7.7,.3 Hz, 2H), 7.72 (ddd, J = 9.3, 2.7,.5 Hz, 2H), 7.39 (td, J = 8.0, 5.4 Hz, H), 2.44 (t, J = 7. Hz, 2H), (m, 2H), (m, 2H), 0.90 (t, J = 7.3 Hz, 3H). C NMR (0 MHz, Chloroform-d) δ 76.8 (d, J = 2.9 Hz), (d, J = 248. Hz), 9.0 (d, J = 6.7 Hz), 4.6 (d, J = 7.5 Hz), (d, J = 2.97 Hz), (d, J = 2.8 Hz), 5.99 (d, J = 23. Hz), 97.56, 79.40, 29.79, 22.09, 8.93,.5. MS (EI, 70 ev): = 203 ([M] -, 0 ), 75 (25), 62 (00), 46 (0), 3 (50), 2 (90), 09 (40), 95 (45), 79 (20), 66 (0), 53 (7). I -(4-Iodophenyl)hept-2-yn--one H NMR (300 MHz, CDCl 3 ) δ 7.84 (m, 4H), 2.50 (t, J = 7.0 Hz, 2H), (m, 2H), (m, 2H), 0.96 (t, J = 7.3 Hz, 3H). C NMR (75 MHz, CDCl 3 ) δ 77.4, 7.8, 6.3, 0.8, 02.3, 97.5, 79.3, 29.8, 22., 8.9,.5. MS (EI, 70 ev): = 32 ([M] +, 00), 283 (40), 270 (00), 24 (0), 23 (90), 203 (5), 57 (5). Br -(4-Bromophenyl)hept-2-yn--one H NMR (300 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 2.50 (t, J = 7.0 Hz, 2H),.66 (m, 2H), (m, 2H), 0.96 (t, J = 7.3 Hz, 3H). C NMR (75 MHz, CDCl 3 ) δ 77., 5.,., 0.0, 29.3, 97.5, 79.4, 29.8, 22., 8.,.5. MS (EI, 70 ev): =265 ([M] -, 0), 237 (0), 222 (00), 93 (0), 85 (96), 67 (8), 57 (60). N 2-(3-Phenylprop-2-yn--yl)-H-indene-,3(2H)-dione

5 H NMR (300 MHz, Chloroform-d) δ 7.82 (dd, J = 5.5, 3. Hz, 2H), 7.66 (dd, J = 5.5, 3. Hz, 2H), (m, 2H), (m, 3H), 4.6 (s, 2H). C NMR (75 MHz, CDCl 3 ) δ 67., 4.3, 2.,.9, 28.5, 28.2, 23., 22.3, 82.9, 82.6, MS (EI, 70 ev): =26 ([M] +, 00), 232 (70), 204 (50), 78 (5), 65 (0), 65 (5). (3-Phenoxyprop--yn--yl)benzene H NMR (300 MHz, Chloroform-d) δ (m, 2H), (m, 5H), (m, 3H), 4.84 (d, J = 0.8 Hz, 2H). C NMR (75 MHz, CDCl 3 ) δ 57.8,.8, 29.5, 28.6, 28.3, 22.3, 2.0, 5.0, 87.0, 83.3, 56.. MS (EI, 70 ev): =208 ([M] +, 5), 5 (00), 05 (5), 89 (3), 65 (5). 3-Phenylprop-2-yn--yl benzoate H NMR (300 MHz, Chloroform-d) δ (m, 2H), (m, H), (m, 4H), (m, 3H), 5.6 (s, 2H). C NMR (75 MHz, CDCl 3 ) δ 65.9, 3.2,.9, 29.8, 29.6, 28.7, 28.4, 28.3, 22.2, 86.6, 83.0, MS (EI, 70 ev): =236 ([M] +, 00), 208 (25), 9 (5).

6 Failed substrates: B B B N N F 3 C B B B H B B B S NC H B B B N H N B B N BF 3 K NH 2 B B B Ph Ph N B B H B N

7 fid Kishore/ NK 074 AuH CDCl3 /opt/topspin fid Kishore/ NK 074 AuC CDCl3 /opt/topspin f (ppm) f (ppm)

8 F 3 C fid Kishore/ NK 075 AuH CDCl3 /opt/topspin f (ppm)

9 Cl fid Kishore/ NK 082 AuH CDCl3 /opt/topspin fid Kishore/ NK 082 AuC CDCl3 /opt/topspin f (ppm) CDCl CDCl CDCl f (ppm)

10 S 4056.f333.0.fid NK083 PRTN CDCl3 {C:\Bruker\TopSpin3.2} f333..fid NK083 CCPD CDCl3 {C:\Bruker\TopSpin3.2} f (ppm) f (ppm)

11 * The peak belongs to side product

12 * The peak belongs to biphenyl

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