Experimental test of the [3+2]- and [2+2]-cycloaddition pathways for the bis-cinchona alkaloid-OsO4 catalyzed dihydroxylation of olefins by means of 12C/13C kinetic isotope effects

Tetrahedron Letters

Volumn 37, Issue 28, 1996, Pages 4899-4902

  Corey, E J ^a   Noe, Mark C ^a   Grogan, Michael J ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; CARBON; CARBON 13; CINCHONA ALKALOID; OSMIUM TETRAOXIDE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; CONTROLLED STUDY; ENANTIOMER; HYDROXYLATION;

EID: 0030575398     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01005-2     Document Type: Article

References (23)

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15. (b) Kinetic isotope effects were calculated using the following equation: (equation presented)
16. 4, filtered and concentrated in vacuo. The substituted styrenes were purified chromatographically. Allyl 4-methoxybenzoate was purified after conversion to the corresponding epoxide.
17. 13C pulses. A 180 second delay between pulses was included to ensure complete relaxation of all carbon atoms. The sweep width was adjusted to allow at least 20 ppm of free space on either edge of the spectral window. Zero filling of the 64K spectrum to 128K afforded a digital resolution of 0.2 Hz/pt for the substituted styrenes and 0.38 Hz/pt for allyl 4-methoxybenzoate. The raw data were processed using trapezoidal multiplication from 0 to 63K, followed by Lorentzian multiplication (LB=Hz/pt), Fourier transformation and zero-order baseline correction. Spectra processed in this manner had measured signal to noise ratios between 40 and 110 and contained between 3 and 5 data points per peak width at half-height. Integration of the signals was carried out so as to include at least 2.6 Hz of baseline on each end of a peak.
18. 13C NMR analysis.
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23. 11. This research was supported by grants from the National Institutes of Health and the National Science Foundation.