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Volumn 65, Issue 26, 2009, Pages 5084-5092

Synthesis of PdII complexes bearing an enantiomerically resolved seven-membered N-heterocyclic carbene ligand and initial studies of their use in asymmetric Wacker-type oxidative cyclization reactions

Author keywords

N Heterocyclic carbene; Organometallic chemistry; Palladium; Wacker oxidation

Indexed keywords

ALKENE; BENZENE DERIVATIVE; N,N' BIS(1 NAPHTHYLMETHYL) 2',2'' DIAMINO M,M QUATERPHENYL; N,N' BIS(CYCLOHEXYLMETHYL) 2',2'' DIAMINO 4',4'' DIMETHYL M,M QUATERPHENYL; PALLADIUM; UNCLASSIFIED DRUG;

EID: 65749112552     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2009.04.072     Document Type: Article
Times cited : (91)

References (57)
  • 4
    • 65749093237 scopus 로고    scopus 로고
    • Chiral bidentate NHCs have been met with more success than chiral monodentate NHCs. As notable examples, see
    • Chiral bidentate NHCs have been met with more success than chiral monodentate NHCs. As notable examples, see:
  • 25
    • 0035906503 scopus 로고    scopus 로고
    • This reaction has also been attempted with other chiral NHCs, albeit with very low enantioselectivity:
    • Lee S., and Hartwig J.F. J. Org. Chem. 66 (2001) 3402-3415 This reaction has also been attempted with other chiral NHCs, albeit with very low enantioselectivity:
    • (2001) J. Org. Chem. , vol.66 , pp. 3402-3415
    • Lee, S.1    Hartwig, J.F.2
  • 40
    • 65749105372 scopus 로고    scopus 로고
    • 2 complexes appears to arise from ortho-metallation of the carboxylate complex. For a more detailed discussion, see: Rogers, M. M. Ph.D. Thesis, University of Wisconsin-Madison, Madison, WI, 2007.
    • 2 complexes appears to arise from ortho-metallation of the carboxylate complex. For a more detailed discussion, see: Rogers, M. M. Ph.D. Thesis, University of Wisconsin-Madison, Madison, WI, 2007.
  • 41
    • 65749083845 scopus 로고    scopus 로고
    • Attempts to resolve amidinium salts with methyl groups in the 3 and 3′ positions of the biphenyl moiety were unsuccessful. For further details, see: Scarborough, C.C. Ph.D. Thesis, University of Wisconsin-Madison, Madison, WI, 2008.
    • Attempts to resolve amidinium salts with methyl groups in the 3 and 3′ positions of the biphenyl moiety were unsuccessful. For further details, see: Scarborough, C.C. Ph.D. Thesis, University of Wisconsin-Madison, Madison, WI, 2008.
  • 42
    • 36749064861 scopus 로고    scopus 로고
    • 7NHCs, Herrmann and co-workers reported that amidinium salts derived from BINAM could be accessed with secondary alkyl and aryl nitrogen substituents when phosgene was added to the mono-formylated diamine: In our hands, these amidinium salts were highly unstable to water and difficult to work with
    • 7NHCs, Herrmann and co-workers reported that amidinium salts derived from BINAM could be accessed with secondary alkyl and aryl nitrogen substituents when phosgene was added to the mono-formylated diamine:. Herrmann W.A., Baskakov D., and Ruhland K. J. Heterocycl. Chem. 44 (2007) 237-239 In our hands, these amidinium salts were highly unstable to water and difficult to work with
    • (2007) J. Heterocycl. Chem. , vol.44 , pp. 237-239
    • Herrmann, W.A.1    Baskakov, D.2    Ruhland, K.3
  • 44
    • 21244438753 scopus 로고    scopus 로고
    • This reaction was inspired by an early report by Tremont and co-workers who reported a Pd-catalyzed ortho methylation of acetanilides using MeI and AgOAc:
    • Daugulis O., and Zaitsev V.G. Angew. Chem., Int. Ed. 44 (2005) 4046-4048 This reaction was inspired by an early report by Tremont and co-workers who reported a Pd-catalyzed ortho methylation of acetanilides using MeI and AgOAc:
    • (2005) Angew. Chem., Int. Ed. , vol.44 , pp. 4046-4048
    • Daugulis, O.1    Zaitsev, V.G.2
  • 48
    • 65749111629 scopus 로고    scopus 로고
    • note
    • Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. 718220 (9), 718221 ((S)-14) and 718222 (19) CCDC. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44-(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk).
  • 51
    • 33344464334 scopus 로고    scopus 로고
    • The use of microwave irradiation to improve reaction times and yields in the synthesis of 5-membered amidinium salts has been demonstrated:
    • The use of microwave irradiation to improve reaction times and yields in the synthesis of 5-membered amidinium salts has been demonstrated:. Aidouni A., Demonceau A., and Delaude L. Synlett (2006) 493-495
    • (2006) Synlett , pp. 493-495
    • Aidouni, A.1    Demonceau, A.2    Delaude, L.3
  • 52
    • 44349094826 scopus 로고    scopus 로고
    • This strategy has also been applied by: In the present case, use of microwave irradiation is critical in obtaining reasonable yields of these 7-membered amidinium salts
    • This strategy has also been applied by:. Luan X., Mariz R., Gatti M., Costabile C., Poater A., Cavallo L., Linden A., and Dorta R. J. Am. Chem. Soc. 130 (2008) 6848-6858 In the present case, use of microwave irradiation is critical in obtaining reasonable yields of these 7-membered amidinium salts
    • (2008) J. Am. Chem. Soc. , vol.130 , pp. 6848-6858
    • Luan, X.1    Mariz, R.2    Gatti, M.3    Costabile, C.4    Poater, A.5    Cavallo, L.6    Linden, A.7    Dorta, R.8
  • 53
    • 65749112749 scopus 로고    scopus 로고
    • Ph.D. Thesis, University of Wisconsin-Madison, Madison, WI
    • Scarborough, C.C. Ph.D. Thesis, University of Wisconsin-Madison, Madison, WI, 2008.
    • (2008)
    • Scarborough, C.C.1
  • 54
    • 65749083083 scopus 로고    scopus 로고
    • note
    • The dimeric catalyst (S,S)-29 was used in conjunction with a silver additive in place of the monomeric catalyst (S)-30 because (S)-30 was prone to decomposition over prolonged storage periods. Control experiments in the cyclization of 2 revealed that the same results are obtained when (S,S)-29 with 4 equiv of AgTFA were employed in the catalytic mixture as when (S)-30 was employed.


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