User menu

Accès à distance ? S'identifier sur le proxy UCLouvain

Palladium-Catalyzed Cyclopropanation of Alkenyl Silanes by Diazo Alkanes: Evidence for a Pd(0) Mechanism.

Primary tabs

Berthon-Gelloz, Guillaume Marchant, Mélanie Straub, Bernd F Marko, Istvan [UCL]

Alkenyl silanes are efficiently converted to the corresponding silyl cyclopropanes in the presence of a slight excess of diazomethane (2-4 equiv) and a low loading of Pd(OAc)(2) (<0.5 mol %). Diazoethane and diazobutane can also be employed and yield silyl cyclopropanes with diastereoselectivities of up to 10:1 for the trans isomer. When conducted on a 4 g scale, the reaction only required a catalyst loading of 5x10(-3) mol %, which corresponds to a turnover frequency of 40 000 h(-1). Competition experiments revealed that vinyl silanes can be selectively cyclopropanated in the presence of an aliphatic terminal alkene and styrene. The complex [Pd(0) (2)(DVTMS)(3)] (38, DVTMS=divinyltetramethyldisiloxane) proved to be an exceptionally active catalyst for the cyclopropanation reaction, giving complete conversion at -35 degrees C in 1 min. Intermolecular and intramolecular competition experiments with DVTMS (36), both with Pd(OAc)(2) and 38, provided strong evidence for a Pd(0)(alkenyl silane)(3) resting state. Detailed density functional calculations on the reaction pathways for the cyclopropanation of trimethylvinylsilane and DVTMS by diazomethane with Pd(0) corroborated the experimental observations.

Document type Article de périodique (Journal article) – Journal Article, Research Support, Non-U.S. Gov't
Publication date 2009
Journal information "Chemistry - A European Journal" - Vol. 15, no. 12, p. 2923-31 (2009)
Peer reviewed yes
e-issn 1521-3765
issn 0441-3776
Publication status Publié
Affiliation UCL - SC/CHIM - Département de chimie
MESH Subject Thermodynamics ; Styrene - chemistry ; Stereoisomerism ; Siloxanes - chemistry ; Silanes - chemistry ; Palladium - chemistry ; Molecular Structure ; Models, Chemical ; Cyclopropanes - chemical synthesis - chemistry ; Cyclization ; Catalysis ; Azo Compounds - chemistry ; Alkenes - chemistry
Links
  1. Pietruszka, Chem. Rev., 103, 1051 (2003)
  2. Salaün, Top. Curr. Chem., 207, 1 (2000)
  3. Rappoport, The Chemistry of the Functional Groups (1987)
  4. Chemistry of the Cyclopropyl Group, Vol. 2 (Ed.: Z. Rappoport), Wiley, New York, 1995.
  5. Lebel, Chem. Rev., 103, 977 (2003)
  6. Lautens, Chem. Rev., 96, 49 (1996)
  7. Doyle, Chem. Rev., 98, 911 (1998)
  8. Charette, Comprehensive Asymmetric Catalysis I-III, Vol. 2, 581 (1999)
  9. Lydon, Comprehensive Asymmetric Catalysis I-III, Vol. 2, 539 (1999)
  10. Pfaltz, Comprehensive Asymmetric Catalysis I-III, Vol. 2, 513 (1999)
  11. Pfaltz, Transition Metals for Organic Synthesis, Vol. 1, 157 (2004)
  12. Rubina, Tetrahedron, 60, 3129 (2004)
  13. Doyle, Modern Rhodium-Catalyzed Organic Reactions, 341 (2005)
  14. Armstrong, J. Org. Chem., 31, 618 (1966)
  15. Paulissen, Tetrahedron Lett., 13, 1465 (1972)
  16. Reiser, Handbook of Organopalladium Chemistry for Organic Synthesis, Vol. 1, 1561 (2002)
  17. Kottwitz, Synthesis, 636 (1975)
  18. Mende, Tetrahedron Lett., 16, 629 (1975)
  19. Nakamura, J. Am. Chem. Soc., 99, 2108 (1977)
  20. Anciaux, J. Org. Chem., 45, 695 (1980)
  21. Suda, Synthesis, 714 (1981)
  22. Abadallah, Tetrahedron Lett., 23, 503 (1982)
  23. Doyle, Organometallics, 3, 44 (1984)
  24. Tomilov, Russ. Chem. Bull., 36, 1234 (1987)
  25. Fontani, Tetrahedron Lett., 30, 4815 (1989)
  26. Shimamoto, J. Org. Chem., 56, 4167 (1991)
  27. Vallgårda, Tetrahedron Lett., 32, 5625 (1991)
  28. Basnak, Synth. Commun., 22, 773 (1992)
  29. Nasim, J. Organomet. Chem., 430, 269 (1992)
  30. Vallgårda, J. Chem. Soc. Perkin Trans. 1, 461 (1994)
  31. Vangveravong, J. Org. Chem., 60, 3409 (1995)
  32. Zaitseva, J. Organomet. Chem., 523, 221 (1996)
  33. Denmark, J. Org. Chem., 62, 3375 (1997)
  34. Luithle, Liebigs Ann., 2297 (1997)
  35. Pietruszka, Synlett, 977 (1997)
  36. Luithle Joachim E. A., Pietruszka Jörg, Witt Andreas, Enantiomerically pure 1,3,2-dioxaborolanes: new reagents for the hydroboration of alkynes, 10.1039/a807163b
  37. Luithle, J. Org. Chem., 64, 8287 (1999)
  38. Pietruszka, J. Chem. Soc. Perkin Trans. 1, 4293 (2000)
  39. Markó, Adv. Synth. Catal., 344, 1063 (2002)
  40. Guseva, Eur. J. Org. Chem., 3136 (2004)
  41. Illa, Organometallics, 26, 3306 (2007)
  42. Bernardi, Organometallics, 20, 2751 (2001)
  43. Rodriguez-Garcia, J. Am. Chem. Soc., 123, 6157 (2001)
  44. Rodriguez-Garcia, Eur. J. Inorg. Chem., 1073 (2000)
  45. Straub, J. Am. Chem. Soc., 124, 14195 (2002)
  46. Markó, Tetrahedron Lett., 43, 2317 (2002)
  47. Heureux, Tetrahedron Lett., 46, 79 (2005)
  48. Fitch, J. Organomet. Chem., 29, 263 (1971)
  49. Fitch, J. Organomet. Chem., 160, 477 (1978)
  50. Mironov, Zh. Obshch. Khim., 45, 1796 (1975)
  51. Schraml Jan, Grignon-dubois Micheline, Dunoguès Jacques, Jancke Harald, Engelhardt Günter, Chvalovský Václav, NMR spectra (13C and 29Si) as a probe into the electronic structure of cyclopropylsilanes, 10.1135/cccc19833396
  52. Hirabayashi, Tetrahedron Lett., 38, 461 (1997)
  53. Berthon-Gelloz, J. Org. Chem., 73, 4190 (2008)
  54. Fitch, Inorg. Chim. Acta, 97, 9 (1985)
  55. Hitchcock, Angew. Chem., 103, 439 (1991)
  56. Angew. Chem. Int. Ed. Engl. 1991, 30, 438.
  57. Krause, J. Am. Chem. Soc., 121, 9807 (1999)
  58. de Vries, Org. Lett., 5, 3285 (2003)
  59. Jaguar 7.0, Schrödinger, New York, NY, 2007;
  60. Becke, J. Chem. Phys., 84, 4524 (1986)
  61. Perdew, Phys. Rev. B, 33, 8822 (1986)
  62. Krishnan, J. Chem. Phys., 72, 650 (1980)
  63. Hay, J. Chem. Phys., 82, 299 (1985)
  64. Schaftenaar, J. Comput.-Aided Mol. Design, 14, 123 (2000)
  65. Defieber, Angew. Chem., 120, 4558 (2008)
  66. Angew. Chem. Int. Ed. 2008, 47, 4482.
  67. Fairlamb, Chem. Eur. J., 12, 8750 (2006)
  68. Pd/DVTMS is commercially available from Umicore A.G.
Bibliographic reference Berthon-Gelloz, Guillaume ; Marchant, Mélanie ; Straub, Bernd F ; Marko, Istvan. Palladium-Catalyzed Cyclopropanation of Alkenyl Silanes by Diazo Alkanes: Evidence for a Pd(0) Mechanism.. In: Chemistry - A European Journal, Vol. 15, no. 12, p. 2923-31 (2009)
Permanent URL http://hdl.handle.net/2078.1/21413