A new chiral titanium species for the ring opening reactions of meso epoxides

Tetrahedron

Volumn 53, Issue 48, 1997, Pages 16545-16552

  Eppley, Alecia W ^a   Totah, Nancy I ^a  

^a E11 SSH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDE; TITANIUM DERIVATIVE;

CAPILLARY GAS CHROMATOGRAPHY; CATALYSIS; CHIRALITY; CONFERENCE PAPER; CONFORMATION; ENANTIOMER; EPOXIDATION; PRIORITY JOURNAL; REACTION ANALYSIS; SYNTHESIS;

EID: 0030731642     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(97)01035-1     Document Type: Conference Paper

References (33)

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19. Though the 2S,3S-epoxide was prepared for this application, either enantiomeric form of this epoxide, and hence either enantiomeric form of ligand 1, is accessible via asymmetric epoxidation of the corresponding allylic alcohol.
20. The abbreviations used to depict protecting groups in this sequence are as follows: tert-butyldimethylsilyl (TBS), ethoxyethyl (EE).
21. 2EtN).
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25. The A value for this substituent is expected to be on the order of 3.0 kcal/mol. As such, relative stereo-control at the spirocenter is achieved by virtue of the anomeric effect.
26. 1H NMR pattern of the C-4 hydrogen. Reduction of ketone 12 with L-Selectride provides exclusively the desired axial alcohol 1.
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29. Optical purity was determined by capillary GC using a chiral Cyclodex B column (J&W Scientific).
30. The anticipated mode of complexation is as indicated in Scheme 2, though the specifics of this structure remain to be elucidated. Note that the ligand 1 is easily recovered in this stoichiometric application by filtration of the crude reaction mixture through a pad of silica, and subsequent elution with ethyl acetate.
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