메뉴 건너뛰기




Volumn 26, Issue 20, 2007, Pages 4863-4865

Catalytic umpolung allylation of aldehydes by π-allylpalladium complexes containing bidentate N-heterocyclic carbene ligands

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; AROMATIC COMPOUNDS; CATALYST ACTIVITY; LIGANDS; OLEFINS; STOICHIOMETRY;

EID: 34948836884     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om700605y     Document Type: Article
Times cited : (70)

References (52)
  • 5
    • 34948896140 scopus 로고    scopus 로고
    • Reference 2a
    • (a) Reference 2a.
  • 8
    • 34250797354 scopus 로고    scopus 로고
    • For a recent review of palladium complexes with NHC ligands, see
    • For a recent review of palladium complexes with NHC ligands, see: Kantchev, E. A. B.; O'Brien, C. J.; Organ, M. G. Angew. Chem., Int. Ed. 2007, 46, 2768-2813.
    • (2007) Angew. Chem., Int. Ed , vol.46 , pp. 2768-2813
    • Kantchev, E.A.B.1    O'Brien, C.J.2    Organ, M.G.3
  • 9
    • 8344265265 scopus 로고    scopus 로고
    • For a review, see
    • For a review, see: Szabó, K. J. Chem.-Eur. J. 2004, 10, 5268-5275.
    • (2004) Chem.-Eur. J , vol.10 , pp. 5268-5275
    • Szabó, K.J.1
  • 12
    • 0037986275 scopus 로고    scopus 로고
    • Allylpalladium complexes ligated by NHC ligands undergo protonolysis reactions with HCl where the allyl ligand presumably acts as a nucleophile: Jensen, D. R, Sigman, M. S. Org. Lett. 2003, 5, 63-65
    • Allylpalladium complexes ligated by NHC ligands undergo protonolysis reactions with HCl where the allyl ligand presumably acts as a nucleophile: Jensen, D. R.; Sigman, M. S. Org. Lett. 2003, 5, 63-65.
  • 13
    • 34948901548 scopus 로고    scopus 로고
    • Yamamoto, Y.; Nakamura, I. In Palladium in Organic Synthesis; Tsuji, J., Ed.; Topics in Organometallic Chemistry 14; Springer-Verlag: New York, 2005; 14, pp 211-239.
    • (a) Yamamoto, Y.; Nakamura, I. In Palladium in Organic Synthesis; Tsuji, J., Ed.; Topics in Organometallic Chemistry 14; Springer-Verlag: New York, 2005; Vol. 14, pp 211-239.
  • 19
    • 34249785407 scopus 로고    scopus 로고
    • For DFT calculations supporting a Sakurai-type mechanism for this reaction, see
    • (c) For DFT calculations supporting a Sakurai-type mechanism for this reaction, see: Piechaczyk, O.; Cantat, T.; Mézailles, N.; Le Floch, P. J. Org. Chem. 2007, 72, 4228-4237.
    • (2007) J. Org. Chem , vol.72 , pp. 4228-4237
    • Piechaczyk, O.1    Cantat, T.2    Mézailles, N.3    Le Floch, P.4
  • 20
    • 33645308290 scopus 로고    scopus 로고
    • For other examples of reactions that are thought to proceed via nucleophilic allylpalladium intermediates, see: (a) Howell, G. P, Minnaard, A. J, Feringa, B. L. Org. Biomol. Chem. 2006, 4, 1278-1283
    • For other examples of reactions that are thought to proceed via nucleophilic allylpalladium intermediates, see: (a) Howell, G. P.; Minnaard, A. J.; Feringa, B. L. Org. Biomol. Chem. 2006, 4, 1278-1283.
  • 23
    • 34948893587 scopus 로고    scopus 로고
    • An alternate strategy developed for palladium-catalyzed umpolung allylation of electrophiles likely involves transmetalation to Zn, B, In, or Sn. For a lead reference, see: Tamaru, Y. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-I, Ed, Wiley-Interscience: New York, 2002; 2, p 1917
    • An alternate strategy developed for palladium-catalyzed umpolung allylation of electrophiles likely involves transmetalation to Zn, B, In, or Sn. For a lead reference, see: Tamaru, Y. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-I., Ed.; Wiley-Interscience: New York, 2002; Vol. 2, p 1917.
  • 24
    • 18444411670 scopus 로고    scopus 로고
    • See Supporting Information for details, (a) Complex 4a: Jones, M. D.; Paz, F. A. A.; Davies. J. E.; Johnson, B. F. G.; Klinowski, J. Acta Crystallogr., Sect. E: Struct. Rep. Online 2003, E59, M538-M540.
    • See Supporting Information for details, (a) Complex 4a: Jones, M. D.; Paz, F. A. A.; Davies. J. E.; Johnson, B. F. G.; Klinowski, J. Acta Crystallogr., Sect. E: Struct. Rep. Online 2003, E59, M538-M540.
  • 25
    • 85152991479 scopus 로고    scopus 로고
    • Complex 4b: Malaisé, G.; Shailesh, R.; Osborn, J. A.; Barloy, L.; Kyritsakas, N.; Graff, R. Eur. J. Inorg. Chem. 2004, 3987-4001.
    • (b) Complex 4b: Malaisé, G.; Shailesh, R.; Osborn, J. A.; Barloy, L.; Kyritsakas, N.; Graff, R. Eur. J. Inorg. Chem. 2004, 3987-4001.
  • 26
    • 31544483930 scopus 로고    scopus 로고
    • Complex 4c: Navarro, O.; Nolan, S. P. Synthesis 2006, 2, 366-367.
    • (c) Complex 4c: Navarro, O.; Nolan, S. P. Synthesis 2006, 2, 366-367.
  • 27
    • 0000004671 scopus 로고    scopus 로고
    • Formation of silver carbenes: Wang, H. M. J.; Lin, I. J. B. Organometallics 1998, 17, 972.
    • (d) Formation of silver carbenes: Wang, H. M. J.; Lin, I. J. B. Organometallics 1998, 17, 972.
  • 28
    • 0042031145 scopus 로고    scopus 로고
    • Counterion exchange: Viciu, M. S.; Kauer, Z. F.; Stevens, E. D.; Nolan, S. P. Organometallics 2003, 22, 3175-3177.
    • (e) Counterion exchange: Viciu, M. S.; Kauer, Z. F.; Stevens, E. D.; Nolan, S. P. Organometallics 2003, 22, 3175-3177.
  • 29
    • 0001474120 scopus 로고    scopus 로고
    • Bidentate NHC ligands and complexes 4d-m: (a) Magill, A. M.; McGuinness, D. S.; Cavell, K. J.; Britovsek, G. J. P.; Gibson, V. C.; White, A. J. P.; Williams, D. J.; White, A. H.; Skelton, B. W. J. Organomet. Chem. 2001, 617-618, 546-560.
    • Bidentate NHC ligands and complexes 4d-m: (a) Magill, A. M.; McGuinness, D. S.; Cavell, K. J.; Britovsek, G. J. P.; Gibson, V. C.; White, A. J. P.; Williams, D. J.; White, A. H.; Skelton, B. W. J. Organomet. Chem. 2001, 617-618, 546-560.
  • 39
    • 34948815751 scopus 로고    scopus 로고
    • Reference 14c
    • (b) Reference 14c.
  • 41
    • 34948908294 scopus 로고    scopus 로고
    • Phosphonium salts, formed by nucleophilic attack of phosphine ligand on the allylpalladium, are formed as the major decomposition products when nucleophilic phosphines are employed
    • Phosphonium salts, formed by nucleophilic attack of phosphine ligand on the allylpalladium, are formed as the major decomposition products when nucleophilic phosphines are employed.
  • 42
    • 34948869980 scopus 로고    scopus 로고
    • Products that would arise from β-hydride elimination of the palladium alkoxide, such as 1-phenyl-3-butenone or 1 -pheny 1-2-butenone, were not observed
    • Products that would arise from β-hydride elimination of the palladium alkoxide, such as 1-phenyl-3-butenone or 1 -pheny 1-2-butenone, were not observed.
  • 43
    • 34948834854 scopus 로고    scopus 로고
    • See reference 3c
    • See reference 3c.
  • 46
    • 0037016413 scopus 로고    scopus 로고
    • For a review of halide effects in transition metal catalysis, see
    • For a review of halide effects in transition metal catalysis, see: Fagnou, K.; Lautens, M. Angew. Chem., Int. Ed. 2002, 41, 26-47.
    • (2002) Angew. Chem., Int. Ed , vol.41 , pp. 26-47
    • Fagnou, K.1    Lautens, M.2
  • 47
    • 2942700115 scopus 로고    scopus 로고
    • The cause of this effect is under investigation and is presumably due to the differing ability of the solvents to coordinate to palladium complex Ih, a Ketz, B. E, Cole, A. P, Waymouth, R. M. Organometallics 2004, 23, 2835-2837
    • The cause of this effect is under investigation and is presumably due to the differing ability of the solvents to coordinate to palladium complex Ih. (a) Ketz, B. E.; Cole, A. P.; Waymouth, R. M. Organometallics 2004, 23, 2835-2837.
  • 49
    • 3042774302 scopus 로고    scopus 로고
    • This trend may be due to the differing rates of transmetalation of the palladium alkoxides with allyltributylstannane. In related allylation reactions a decrease in rate with increasing electron-donating ability of pincer ligands has been attributed to a decrease in the rate of transmetalation: Solin, N, Kjellgren, J, Szabó, K. J. J. Am. Chem. Soc. 2004, 126, 7026-7033
    • This trend may be due to the differing rates of transmetalation of the palladium alkoxides with allyltributylstannane. In related allylation reactions a decrease in rate with increasing electron-donating ability of pincer ligands has been attributed to a decrease in the rate of transmetalation: Solin, N.; Kjellgren, J.; Szabó, K. J. J. Am. Chem. Soc. 2004, 126, 7026-7033.
  • 50
    • 34948812656 scopus 로고    scopus 로고
    • At this time we are unable to rule out an alternate Sakurai-type mechanism, where the palladium complex functions as a Lewis acid catalyst to activate the aldehyde toward addition of allylstannane, a For a discussion, see ref 10c
    • At this time we are unable to rule out an alternate Sakurai-type mechanism, where the palladium complex functions as a Lewis acid catalyst to activate the aldehyde toward addition of allylstannane. (a) For a discussion, see ref 10c.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.