C.R. Smith, T.V. RajanBabu / Tetrahedron 66 (2010) 1102–1110
1109
1H), 7.60 (d, J¼7.00 Hz, 1H), 7.42 (t, J¼8.00 Hz, 1H), 6.75 (dd,
J¼17.50, 11.00 Hz, 1H), 5.83 (d, J¼17.50 Hz, 1H), 5.33 (d, J¼11.00 Hz,
Supplementary data
1H), 2.61 (s, 3H). 13C NMR (125 MHz, CDCl3):
d
198.0 138.0, 137.4,
Full experimental details, copies of all NMR spectra (1H and 13C),
and chromatograms. Supplementary data associated with this ar-
135.9,130.5,128.7,127.6,126.0,115.2, 26.6. HRMS-ESI: m/z [MþNa]þ
Calcd for C9H8OþNa: 155.0467; found: 155.0468. Rf¼0.32 (hex-
anes–EtOAc, 9:1). GC [poly(dimethylsiloxane)] conditions: 30 min
at 135 ꢀC; retention time (min): 12.44.
References and notes
1. (a) Heck, R. F. J. Am. Chem. Soc. 1968, 90, 5518; (b) Mizoroki, T.; Mori, K.; Ozaki, A.
Bull. Chem. Soc. Jpn. 1971, 44, 581; (c) Braese, S.; de Meijere, A. In Metal-Cata-
lyzed Cross-Coupling Reactions; de Meijere, A., Diederich, F., Eds.; Wiley-VCH:
Weinheim, 2004; pp 217–315; (d) Beller, M.; Zapf, A.; Riemeier, T. H. In Tran-
sition Metals for Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH:
Weinheim, 2004; pp 271–305; (e) Beletskaya, I. P.; Cheprakov, V. Chem. Rev.
2000, 100, 3009; (f) Farina, V. Adv. Synth. Catal. 2004, 346, 1553.
4.3.26. 1-Phenyl-1,3-butadiene (37).
(500 MHz, CDCl3):
Clear liquid. 1H NMR
7.41 (d, J¼7.50 Hz, 2H), 7.32 (t, J¼8.00 Hz, 2H), 7.23
d
(t, J¼7.50 Hz, 1H), 6.80 (dd, J¼16.00, 10.00 Hz, 1H), 6.57 (d, J¼16.00 Hz,
1H), 6.54–6.50 (m, 1H), 5.34 (d, J¼17.00 Hz, 1H), 5.18 (d, J¼10.00 Hz,
2. Grubbs, R. H. Tetrahedron 2004, 60, 7117.
3. Epoxidation: (a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974; (b)
Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112,
2801; Hydroformylation: (c) Parrinello, G.; Stille, J. K. J. Am. Chem. Soc. 1987, 109,
7122; (d) Agbossou, F.; Carpentier, J.-F.; Mortreux, A. Chem. Rev. 1995, 95, 2485;
Hydrosilylation: (e) Yamamoto, K.; Hayashi, T.; Kumada, M. J. Am. Chem. Soc.
1971, 93, 5301; (f) Hatanaka, Y.; Goda, K.; Yamashita, F.; Hiyama, T. Tetrahedron
Lett. 1994, 35, 7981; Hydroamination: (g) Mu¨ller, T. E.; Hultsch, K. C.; Yus, M.;
Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795; (h) Utsunomia, M.; Hartwig, J.
F. J. Am. Chem. Soc. 2003, 125, 14286; Hydrocyanation: (i) Casalnuovo, A. L.;
RajanBabu, T. V.; Ayers, T. A.; Warren, T. J. Am. Chem. Soc. 1994, 116, 9869; (j)
RajanBabu, T. V.; Casalnuovo, A. L. J. Am. Chem. Soc. 1996, 118, 6325.
4. (a) Nomura, N.; Jin, J.; Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 1998, 120, 459;
(b) Zhang, A.; RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 54; (c) Zhang, A.;
RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 5620; (d) Smith, C. R.; RajanBabu, T.
V. Org. Lett. 2008, 10, 1657; (e) For a recent review, see: RajanBabu, T. V. Synlett
2009, 853.
1H). 13C NMR (125 MHz, CDCl3):
d 137.2,137.1,132.8,129.6,128.6,127.6,
126.4, 117.6. HRMS-ESI: m/z [M]þ Calcd for C10H10: 130.0777; found:
130.0773. Rf¼0.40 (isocratic n-pentane). GC [poly(dimethylsiloxane)]
conditions: 30 min at 100 ꢀC; retention time (min): 20.04.
4.3.27. 4-tert-Butyl-1-vinylcyclohex-1-ene (38).
NMR (500 MHz, CDCl3):
Clear liquid. 1H
d
6.36 (dd, J¼17.50, 10.50 Hz, 1H), 5.76 (t,
J¼3.00 Hz, 1H), 5.06 (d, J¼17.50 Hz, 1H), 4.89 (d, J¼10.50 Hz, 1H),
2.36–2.30 (m, 1H), 2.20–2.14 (m, 1H), 2.10–2.02 (m, 1H), 1.94–1.88
(m, 2H), 1.32–1.26 (m, 1H), 1.18 (ddd, J¼12.00, 8.00, 5.00 Hz, 1H),
5. (a) Hofmann, A. W. Liebigs Ann. Chem. 1851, 78, 253; (b) Brewster, J. H.; Eliel, E. L.
Org. React. 1953, 7, 99; (c) Wu, S. L.; Tao, Y. T.; Saunders, W. H., Jr. J. Am. Chem.
Soc. 1984, 106, 7583.
0.89 (s, 9H). 13C NMR (125 MHz, CDCl3):
d 139.7, 136.0, 130.0, 109.8,
6. (a) Matteson, D. S. J. Am. Chem. Soc. 1960, 82, 4228; (b) Kerins, F.; O’Shea, D. F. J.
Org. Chem. 2002, 67, 4968; (c) Peyroux, E.; Berthiol, F.; Doucet, H.; Santelli, M.
Eur. J. Org. Chem. 2004, 1075; (d) Darses, S.; Michaud, G.; Genet, J.-P. Eur. J. Org.
Chem. 1999, 1875; (e) Darses, S.; Michaud, G.; Genet, J.-P. Tetrahedron Lett. 1998,
39, 5045; (f) Stewart, S. K.; Whiting, A. J. Organomet. Chem. 1994, 482, 293; (g)
Lightfoot, A. P.; Twiddle, S. J. R.; Whiting, A. Synlett 2005, 529; (h) Molander, G.
A.; Rivero, M. R. Org. Lett. 2002, 4, 107; (i) Molander, G. A.; Brown, A. R. J. Org.
Chem. 2006, 71, 9681; (j) Joucla, L.; Cusati, G.; Pinel, C.; Djakovitch, L. Tetra-
hedron Lett. 2008, 49, 4378.
7. (a) Denmark, S. E.; Butler, C. R. Org. Lett. 2006, 8, 63; (b) Denmark, S. E.; Wang, Z.
Synthesis 2000, 999; (c) Denmark, S. E.; Wang, Z. J. Organomet. Chem. 2001, 624,
372; (d) Hatanaka, Y.; Hiyama, T. J. Org. Chem. 1988, 53, 918.
8. (a) Littke, A. F.; Schwartz, L.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 6343; (b)
Grasa, G. A.; Nolan, S. P. Org. Lett. 2001, 3, 119; (c) McKean, D. R.; Parrinello, G.;
Renaldo, A. F.; Stille, J. K. J. Org. Chem. 1987, 52, 422; (d) Shirakawa, E.; Yamasaki,
K.; Tamerjiro, H. Synthesis 1998, 1544; (e) Krolski, M. E.; Renaldo, A. F.; Rudisill,
D. E.; Stille, J. K. J. Org. Chem. 1988, 53, 1170.
9. (a) Tamao, K.; Sumitani, K.; Kiso, Y.; Zembayashi, M.; Fujioka, A.; Kodama, S.;
Nakajima, I.; Minato, A.; Kumada, M. Bull. Chem. Soc. Jpn. 1976, 49, 1958; (b)
Nugent, W. A.; McKinney, R. J. J. Org. Chem. 1985, 50, 5370; (c) Bumagin, N. A.;
Luzikova, E. V. J. Organomet. Chem. 1997, 532, 271.
10. (a) Plevyak, J. E.; Heck, R. F. J. Org. Chem. 1978, 43, 2454; For a recent report on
the use of ligand-free Pd salts, see: (b) de Vries, A. H. M.; Mulders, J. M. C. A.;
Mommers, J. H. M.; Henderickx, H. J. M.; de Vries, J. G. Org. Lett. 2003, 5, 3285
and references cited therein.
44.3, 32.2, 27.4, 27.2, 25.2, 23.7. HRMS-ESI: m/z [M]þ Calcd for
C12H20: 164.1560; found: 164.1558. Rf¼0.76 (isocratic n-pentane).
GC [poly(dimethylsiloxane)] conditions: 30 min at 130 ꢀC; re-
tention time (min): 12.51.
O
O
4.3.28. Methyl 2,4-pentadienoate (39).
(400 MHz, CDCl3):
Clear liquid. 1H NMR
d
7.22 (dd, J¼15.20, 10.40 Hz, 1H), 6.41 (dt,
J¼17.20, 10.80 Hz, 1H), 5.86 (d, J¼15.20 Hz, 1H), 5.55 (d, J¼17.20 Hz,
1H), 5.44 (d, J¼10.00 Hz,1H), 3.70 (s, 3H).13C NMR (100 MHz, CDCl3):
d
167.1, 144.7, 134.6, 125.5, 121.6, 51.4. HRMS-ESI: m/z [MþNa]þ Calcd
for C6H8O2þNa: 135.0416; found: 135.0411. Rf¼0.32 (hexanes–
EtOAc, 9:1). GC [poly(dimethylsiloxane)] conditions: 30 min at
70 ꢀC; retention time (min): 7.90 (Z), 8.94 (E); 3:97.
11. Spencer, A. J. Organomet. Chem. 1983, 258, 101.
12. A recent review of palladacycles: Dupont, J.; Consorti, C. S.; Spencer, J. Chem.
Rev. 2005, 105, 2527.
4.3.29. 1-Vinylcyclohex-1-ene (40).
(400 MHz, CDCl3):
6.35 (dd, J¼17.60, 10.80 Hz, 1H), 5.77 (s, 1H), 5.07
(d, J¼17.60 Hz, 1H), 4.90 (d, J¼10.80 Hz, 1H), 2.14 (d, J¼4.40 Hz, 4H),
1.72–1.60 (m, 4H). 13C NMR (100 MHz, CDCl3):
140.2, 136.0, 129.8,
109.5, 25.8, 23.8, 22.5, 22.4. HRMS-ESI: m/z [M]þ Calcd for C8H12
Clear liquid. 1H NMR
13. (a) Herrmann, W. A.; Brossmer, C.; Ofele, K.; Reisinger, C. P.; Priermeier, T.;
Beller, M.; Fischer, H. Angew. Chem., Int. Ed. Engl. 1995, 34, 1844; (b) Beller, M.;
Tafesh, A.; Herrmann, W. A. German Patent DE 19,503,119, 1996. (c) Herrman,
W. A.; Bo¨hm, V. P. W.; Reisinger, C.-P. J. Organomet. Chem. 1999, 576, 23; (d) Atla,
S. B.; Kelkar, A. A.; Puranik, V. G.; Bensch, W.; Chaudhari, R. V. J. Organomet.
Chem. 2009, 694, 683.
d
d
:
14. Alonso, D. A.; Na´jera, C.; Pacheco, M. C. Adv. Synth. Catal. 2002, 344, 172.
15. (a) Onoue, H.; Minami, K.; Nakagawa, K. Bull. Chem. Soc. Jpn. 1970, 43, 3480; (b)
Beletskaya, I. P.; Kashin, A. N.; Karlstedt, N. B.; Mitin, A. V.; Cheprakov, A. V.;
Kazankov, G. M. J. Organomet. Chem. 2001, 622, 89; (c) Bedford, R. B.; Cazin, C. S.
J.;Coles, S.J.;Gelbrich, T.;Hursthouse, M. B.;Scordia, V. J. M. DaltonTrans. 2003, 3350;
(d) Gavin, L. E.; David, B.; Glen, B. D.; Laurence, P. G. W. Can. J. Chem. 2005, 83, 980.
16. (a) Cameron, N. D.; Kilner, M. J. Chem. Soc., Chem. Commun. 1975, 687; (b)
Horino, H.; Inone, N. J. Org. Chem. 1981, 46, 4416.
108.0935; found: 108.0938. Rf¼0.94 (isocratic n-pentane). GC [poly-
(dimethylsiloxane)] conditions: 30 min at 60 ꢀC; retention time (min):
18.10.
Acknowledgements
17. (a) Shaw, B. L.; Perera, S. D.; Staley, E. A. Chem. Commun. 1998, 1361; (b) Al-
bisson, D. A.; Bedford, R. B.; Scully, P. N. Tetrahedron Lett. 1998, 39, 9793.
18. (a) Dupont, J.; Beydoun, N.; Pfeffer, M. J. Chem. Soc., Dalton Trans. 1989, 1715; (b)
Dupont, J.; Basso, N. R.; Meneghetti, M. R.; Konrath, R. A.; Burrow, R.; Horner, M.
Organometallics 1997, 16, 2386.
Financial assistance for this research by NSF (CHE-0610349) and
NIH (General Medical Sciences, R01 GM075107) is gratefully
acknowledged. We also thank the ACS Organic Division for a grad-
uate fellowship sponsored by the Schering-Plough Corporation to
Craig R. Smith.
´
19. (a) Alonso, D. A.; Najera, C.; Pacheco, C. Org. Lett. 2000, 2, 1823; (b) Botella, L.;
Na´jera, C. Angew. Chem., Int. Ed. 2002, 41, 179; (c) Alonso, D. A.; Na´jera, C.;