Mechanism for the Heck Reaction：对Heck反应机理.doc

Supporting InformationCe0.98Pd0.02O2-d: Recyclable, Ligand Free Palladium(II) Catalyst for Heck Reaction Sanjaykumar S Ra, Bhaskar Devu Mukria, Satish Patila, Giridhar Madrasb and M S Hegde*aa Solid State Structural Chemistry Unit, Indian Institute of Science, Bangalore, India. PIN 560012b Department of Chemical Engineering, Indian Institute of Science, Bangalore, India. PIN 560012* To whom correspondence should be addressedProf. M. S. Hegde (E-mail: mshegdesscu.iisc.ernet.in)NMR datas of the compounds:(E)-tert-butyl cinnamate: (Sn -1)Colorless liquid; yield 82.49 %; 1H NMR (400 MHz, CDCl3) 7.538 7.498 (d, J = 16 Hz, 1H), 7.451 7.429 (m, 2H), 7.306 7.289 (m, 2H), 6.321 6.281 (d, J = 16 Hz, 1H), 1.466 (s, 9H); 13C NMR (100 MHz, CDCl3) 166.34, 143.54, 134.65, 129.93, 128.79, 127.94, 120.16, 80.51, 28.18, (E)-ethyl cinnamate: ( Sn- 4) Colorless liquid; yield 83.01 %; 1H NMR (400 MHz, CDCl3) - 7.622 7.582 (d, J=16 Hz, 1H), 7.442 7.418 (m, 2H), 7.299 7.276 (m, 2H), 6.372 6.332 (d, J = 16 Hz, 1H), 4.185 4.168 (q, J = 6.8 Hz, 2H), 1.266 1.230 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) 167.02, 144.61, 134.50, 130.25, 128.90, 128.08, 118.31, 60.52, 14.36.(E)-methyl cinnamate: (Sn -5) Colourless Liquid; yield 86.98 %; 1H NMR (400 MHz, CDCl3) 7.72 7.68 (d, J = 16 Hz, 1H), 7.535 7.511 (m, 2H), 7.401 7.373 (m, 2H), 6.466 6.426 (d, J = 16 Hz, 1H), 3.807 (s, 3H); 13C NMR (100 MHz, CDCl3) 167.36, 144.81, 134.32, 130.23, 128.82, 128.01, 117.74, 51.62.(E)-tert-butyl 3-(4-formylphenyl)acrylate: (Sn-8)Colorless liquid; yield 95.22 %; 1H NMR (400 MHz, CDCl3) 9.950 (s, 1H), 7.826 7.806 (d, J = 8 Hz, 2H), 7.596 7.575 (d, J = 8.4 Hz, 2H), 7.556 7.516 (d, J = 16 Hz, 1 H), 1.471 (s, 9H); 13C NMR (100 MHz, CDCl3) 191.46, 165.61, 141.76, 140.39, 136.94, 130.11, 128.36, 123.41, 81.05, 28.12. (E)-ethyl 3-(4-hydroxyphenyl)acrylate: (Sn-10)Colorless liquid; yield 52.02 %; 1H NMR (400 MHz, CDCl3) 7.657 7.617 (d, J = 16 Hz, 1H), 7.401 7.385 (d, J = 6.4 Hz, 2H), 7.208 (s, 1H), 6.888 6.867 (d, J = 8.4 Hz, 2H), 6.308 6.268 (d, J = 16 Hz, 1 H), 4.299 4.246 (q, J = 7.2 Hz, 2 H), 1.35 1.32 (t, J = 8 Hz, 3H); 13C NMR (100 MHz, CDCl3) 168.33, 158.43, 145.11, 126.64, 155.95, 144.94, 60.75, 14.22.(E)-1,2-diphenylethene:(Sn- 3) Colorless Solid, mp 122o C; yield 63.85 %; 1H NMR (400 MHz, CDCl3) 7.677 7.674 (d, 4H), 7.654 7.487 (m, 4H), 7.427 7.381 (m, 2H), 7.26 (s, 2H); 13C NMR (100 MHz, CDCl3) 137.30, 128.67, 128.65, 127.59, 126.49(E)-ethyl 3-(thiophen-2-yl)acrylate: (Sn -14)Colorless liquid; yield 87.77 %; 1H NMR (400 MHz, CDCl3) 7.800 7.761 (d, J = 15.6 Hz, 1H), 7.372 7.360 (d, J = 4.8 Hz, 1H), 7.253 7.243 (d, J = 4 Hz, 1H), 7.059 7.037 (m, 1H), 6.259 6.220 (d, J = 15.6 Hz, 1H), 4.275 4.222 (q, J = 8.8 Hz, 2H), 1.343 1.308 (t, J = 14 Hz, 3H); 13C NMR (100 MHz, CDCl3) 166.80, 139.64, 136.97, 130.67, 128.27, 128.03, 117.13, 60.45, 29.68, 14.31.(E)-tert-butyl 3-p-tolylacrylate: (Sn -71)Colorless liquid; yield 46.21 %; 1H NMR (400 MHz, CDCl3) 7.578 7.538 (d, J = 16 Hz, 1H), 7.401 7.381 (d, J = 8 Hz, 2H), 7.171 7.151 (d, J = 8 Hz, 2H), 6.337 6.297 (d, J = 16 Hz, 1H), 2.351 (s, 3H), 1.529 (s, 9H); 13C NMR (100 MHz, CDCl3) 166.46, 143.48, 140.21, 131.92, 129.50, 127.89, 119.09, 80.26, 28.18, 21.35. (E)-tert-butyl 3-(4-aminophenyl)acrylate: ( Sn 72)Colorless liquid; yield 65.23 %; 1H NMR (400 MHz, CDCl3) 7.515 7.475 (d, J = 16 Hz, 1H), 7.331 7.310 (d, J = 8.4, 2 H), 6.641 6.620 (d, J = 8.4 Hz, 2H), 3.909 (s, 1H), 1.519 (s, 9H); 13C NMR (100 MHz, CDCl3) 167.02, 148.40, 143.77, 129.64, 124.90, 115.68, 114.78, 79.90, 28.21. (E)-methyl 3-p-tolylacrylate: ( Sn -75) Colorless liquid; yield 48.56 %; 1H NMR (400 MHz, CDCl3) 7.687 7.647 (d, J = 16 Hz, 1H), 7.424 7.403 (d, J = 8.4 Hz, 2H), 7.193 7.173 (d, J = 8 Hz, 2H), 6.410 6.370 (d, J = 16 Hz, 1H), 3.79 (s, 3H), 2.366 (s, 3H); 13C NMR (100 MHz, CDCl3) 167.57, 144.83, 140.66, 131.66, 129.58, 128.03, 116.70, 51.32, 29.66, 21.40. (E)-tert-butyl 3-(thiophen-3-yl)acrylate: (Sn -80)Colorless liquid; yield 83.23 %; 1H NMR (400 MHz, CDCl3) 7.585 7.546 (d, J = 15.6 Hz, 1H), 7.452 7.445 (m, 1H), 7.322 7.302 (m, 1H), 7.277 7.261 (m, 1H), 6.211 6.172 (d, J = 15.6 Hz, 1.524 (s, 3H); 13C NMR (100 MHz, CDCl3) 166.50, 137.74, 137.02, 127.37, 126.74, 125.17, 119.88, 80.37, 28.18. (E)-tert-butyl 3-(pyridin-2-yl)acrylate: (Sn 79)Colorless oil; yield 84.65 %; 1H NMR (400 MHz, CDCl3) 8.633 8.626 (d, J = 2.4 Hz, 1H), 7.707 7.673 (m, 1H), 7.604 7.565 (d, J = 15.6 Hz, 1H), 7.423 7.404 (d, J = 7.6 Hz, 1H), 7.257 7.223 (m,1H), 6.846 6.806 (d, J = 16 Hz, 1H), 1.532 (s, 9H); 13C NMR (100 MHz, CDCl3) 165.93, 153.42, 149.99, 142.15, 136.69, 124.73, 123.68, 80.72, 28.18. (E)-tert-butyl 3-(pyridin-3-yl)acrylate: ( Sn -78)Colorless oil; yield 96.12 %; 1H NMR (400 MHz, CDCl3) 8.644 (s, 1H), 8.498 8.487 (d, J = 4.4 Hz, 1H), 7.744 7.721 (m, 1H), 7.499 7.459 (d, J = 16 Hz, 1H), 7.250 7.207 (m, 1H), 6.375 6.334 (d, J = 16.4 Hz, 1H), 1.452 (s, 9H); 13C NMR (100 MHz, CDCl3) 165.34, 150.52, 149.41, 139.59, 133.96, 130.38, 123.49, 122.41, 80.75, 28.03. (E)-tert-butyl 3-(naphthalen-5-yl)acrylate: (Sn -83)Colorless oil; yield 93.52 %; 1H NMR (400 MHz, CDCl3) 7.797 7.795 (d, J = 15.6 Hz, 1H), 8.121 8.100(d, J = 8.4 Hz, 1H), 7.797 7.770 (m, 2H), 7.659 7.641 (d, J = 7.2 Hz, 1H), 7.502 7.414 (