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Volumn 121, Issue 26, 1999, Pages 6258-6268

Enantioselective Ti(IV) sulfoxidation catalysts bearing C3-symmetric trialkanolamine ligands: Solution speciation by 1H NMR and ESI-MS analysis

Author keywords

[No Author keywords available]

Indexed keywords

ALKANOLAMINE; TITANIUM DERIVATIVE;

EID: 0033532953     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983569x     Document Type: Article
Times cited : (84)

References (53)
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    • Derivatives of tartaric acid were employed in refs 7-12 and 18, 1,1′-binaphthol and its derivatives in refs 13 and 14, and 1,2-diaryl and di-tert-butylethane-1,2-diols in refs 15-17
    • Derivatives of tartaric acid were employed in refs 7-12 and 18, 1,1′-binaphthol and its derivatives in refs 13 and 14, and 1,2-diaryl and di-tert-butylethane-1,2-diols in refs 15-17.
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    • Johnson, R. A.; Sharpless, K. B. In ref la. Chapter 4.1, pp 103-158
    • Johnson, R. A.; Sharpless, K. B. In ref la. Chapter 4.1, pp 103-158.
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    • 1H NMR spectra have been recorded at low temperature in order to shift the resonance of the free hydroxy group in a region far away from the signals of interest. At -10°C, it was observed at 1.65 ppm (see Figure 1, spectrum a)
    • 1H NMR spectra have been recorded at low temperature in order to shift the resonance of the free hydroxy group in a region far away from the signals of interest. At -10°C, it was observed at 1.65 ppm (see Figure 1, spectrum a).
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    • Stock solutions of chloroform (stabilized with silver foils) were routinely used with no acidic additives
    • Stock solutions of chloroform (stabilized with silver foils) were routinely used with no acidic additives.
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    • Variation of the spray voltage (2-7 kV), of the capillary voltage (10-50 V), and of the temperature (80-180°C) does not affect the speciation pattern in the in situ 2a system
    • Variation of the spray voltage (2-7 kV), of the capillary voltage (10-50 V), and of the temperature (80-180°C) does not affect the speciation pattern in the in situ 2a system.
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    • The location of the protonation site in ions III, IV, V, XI, and XII cannot be precisely assigned via ESI-MS. We will assume that the protonation occurs at the nitrogen atom of the apical trialkanolamine ligand
    • The location of the protonation site in ions III, IV, V, XI, and XII cannot be precisely assigned via ESI-MS. We will assume that the protonation occurs at the nitrogen atom of the apical trialkanolamine ligand.
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    • 1H NMR spectra reported in Figure 1S, Supporting Information).
    • 1H NMR spectra reported in Figure 1S, Supporting Information).
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    • The achiral peroxo complex 4c is unstable at 21°C and decomposes readily in the presence of an excess of TBHP
    • The achiral peroxo complex 4c is unstable at 21°C and decomposes readily in the presence of an excess of TBHP.
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    • The calculated geometrical parameters for peroxide 4a are comparable with previously reported data for Ti(IV) trialkanolamine complexes from difrattometric analysis (see refs 24 and 25) and calculations performed on other monomeric transition metal peroxides; see: (a) Bonchio, M.; Di Furia, F.; Licini, G.; Modena, G.; Moro, S.; Nugent, W. A. J. Am. Chem. Soc. 1997, 119, 6935.
    • (1997) J. Am. Chem. Soc. , vol.119 , pp. 6935
    • Bonchio, M.1    Di Furia, F.2    Licini, G.3    Modena, G.4    Moro, S.5    Nugent, W.A.6
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    • The optimized geometries of complex (S,S,S)-4a and of the isomers A-D of ion XIII are reported in the Supporting Information, Figure S2
    • The optimized geometries of complex (S,S,S)-4a and of the isomers A-D of ion XIII are reported in the Supporting Information, Figure S2.
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    • note
    • 2 experiments. Indeed, elongation of the O - t-Bu bond occurring in B could explain the loss of the isobutene residue hypothesized in Figure 11.
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    • (1974) The Chemistry of Thiol Group , Issue.2 PART , pp. 721-784
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    • Ion likely originating from the reaction of ion X with neutral solvent molecules (methanol) (see also ref 33)
    • Ion likely originating from the reaction of ion X with neutral solvent molecules (methanol) (see also ref 33).


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