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Volumn 80, Issue 5, 2008, Pages 967-977

Enantio- and regioselective CpRu-catalyzed Carroll rearrangement

Author keywords

Allyl complexes; Enantioselective catalysis; Hexacoordinated phosphorus; N ligands; Ruthenium

Indexed keywords


EID: 44649137835     PISSN: 00334545     EISSN: None     Source Type: Journal    
DOI: 10.1351/pac200880050967     Document Type: Conference Paper
Times cited : (22)

References (74)
  • 37
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    • For a Pd-catalyzed enantioselective Carroll rearrangement, see
    • For a Pd-catalyzed enantioselective Carroll rearrangement, see: R. Kuwano, N. Ishida, M. Murakami. Chem. Commun. 3951 (2005).
    • (2005) Chem. Commun , vol.3951
    • Kuwano, R.1    Ishida, N.2    Murakami, M.3
  • 38
    • 4344566130 scopus 로고    scopus 로고
    • For a general review on asymmetric allylic alkylation, see
    • For a general review on asymmetric allylic alkylation, see: B. M. Trost. J. Org. Chem. 69, 5813 (2004).
    • (2004) J. Org. Chem , vol.69 , pp. 5813
    • Trost, B.M.1
  • 42
    • 4344614048 scopus 로고    scopus 로고
    • Ligand 8 was still unable to accelerate the reaction catalyzed by 1b under the optimized conditions (0 % conv., 7d, THF, 60 °C, 0.5 M); compound 1b being prepared using Kündig's protocol: E. P. Kündig, F. R. Monnier. Adv. Synth. Catal. 346, 901 (2004).
    • Ligand 8 was still unable to accelerate the reaction catalyzed by 1b under the optimized conditions (0 % conv., 7d, THF, 60 °C, 0.5 M); compound 1b being prepared using Kündig's protocol: E. P. Kündig, F. R. Monnier. Adv. Synth. Catal. 346, 901 (2004).
  • 43
    • 44649162934 scopus 로고    scopus 로고
    • The enantiopure primary amines were commercially available or readily prepared following literature precedents, R-1,2-diphenylethanamine was obtained from the racemate using a semi-preparative CSP-HPLC resolution (Chiralpak IA, For the synthesis and absolute configuration assignment, see (a) T. Asai, T. Aoyama, T. Shioiri. Synthesis 811 (1980);
    • The enantiopure primary amines were commercially available or readily prepared following literature precedents. (R)-1,2-diphenylethanamine was obtained from the racemate using a semi-preparative CSP-HPLC resolution (Chiralpak IA). For the synthesis and absolute configuration assignment, see (a) T. Asai, T. Aoyama, T. Shioiri. Synthesis 811 (1980);
  • 45
    • 0000095606 scopus 로고    scopus 로고
    • (R)-2,2-dimethyl-1-phenyl-propan-1-amine: M. E. Warren, H. E. Smith. J. Am. Chem. Soc. 87, 1757 (1965);
    • (c) (R)-2,2-dimethyl-1-phenyl-propan-1-amine: M. E. Warren, H. E. Smith. J. Am. Chem. Soc. 87, 1757 (1965);
  • 48
    • 44649199563 scopus 로고    scopus 로고
    • The o-MeO substituent in 9h creates an A(1,3) strain situation with the neighboring stereogenic center; the increased rigidity of 9h vs. 9g is possibly the reason for the better selectivity. With the MeO group, 9h is also a potential tridentate ligand; the ether linkage functioning possibly as an on-off-ligand allowing for the formation of a σ-allyl Ru-intermediate. We thank a referee for this latter suggestion
    • The o-MeO substituent in 9h creates an A(1,3) strain situation with the neighboring stereogenic center; the increased rigidity of 9h vs. 9g is possibly the reason for the better selectivity. With the MeO group, 9h is also a potential tridentate ligand; the ether linkage functioning possibly as an "on-off"-ligand allowing for the formation of a σ-allyl Ru-intermediate. We thank a referee for this latter suggestion.
  • 55
    • 44649150814 scopus 로고    scopus 로고
    • TRISPHAT-N: [bis(tetrachlorobenzenediolato)mono(5-chloropyridine-2,3- diolato) phosphate(V)] anion. This anion 11 is chiral and was used as a racemate throughout this study.
    • TRISPHAT-N: [bis(tetrachlorobenzenediolato)mono(5-chloropyridine-2,3- diolato) phosphate(V)] anion. This anion 11 is chiral and was used as a racemate throughout this study.
  • 56
    • 44649162178 scopus 로고    scopus 로고
    • 6].
    • 6].
  • 57
    • 44649166666 scopus 로고    scopus 로고
    • Compound 12 has been fully characterized using classical spectroscopic and spectrometric means. See the supplementary material.
    • Compound 12 has been fully characterized using classical spectroscopic and spectrometric means. See the supplementary material.
  • 58
    • 44649194771 scopus 로고    scopus 로고
    • In the absence of 3b or 12, allylic ester 4a is thermally stable at 140 °C for at least 2 h with no trace of 12 or other isomers being observed: see Table 3, entry 1
    • In the absence of 3b or 12, allylic ester 4a is thermally stable at 140 °C for at least 2 h with no trace of 12 or other isomers being observed: see Table 3, entry 1.
  • 60
    • 0032275476 scopus 로고    scopus 로고
    • Bimetallic complexes can be extremely effective catalysts in a variety of processes, see: a
    • Bimetallic complexes can be extremely effective catalysts in a variety of processes, see: (a) B. Coq, F. Figueras. Coord. Chem. Rev. 178-180, 1753 (1998);
    • (1998) Coord. Chem. Rev , vol.178-180 , pp. 1753
    • Coq, B.1    Figueras, F.2
  • 63
    • 44649121811 scopus 로고    scopus 로고
    • Compound 13, its enantiomer or the racemate, have been used successfully as ligands in many metal-catalyzed processes, see: (a) T. J. Goodwin, R. S. Vagg, P. A. Williams. J. Proc R. Soc. N. S. W. 117, 1 (1984);
    • Compound 13, its enantiomer or the racemate, have been used successfully as ligands in many metal-catalyzed processes, see: (a) T. J. Goodwin, R. S. Vagg, P. A. Williams. J. Proc R. Soc. N. S. W. 117, 1 (1984);
  • 74
    • 44649121195 scopus 로고    scopus 로고
    • This result reflects the intrinsic instability of ligand 13 and its complexes 14. For this reason, recycling of complexes 15 or reactions under microwave irradiation was not attempted
    • This result reflects the intrinsic instability of ligand 13 and its complexes 14. For this reason, recycling of complexes 15 or reactions under microwave irradiation was not attempted.


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