Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 11, Issue 18, Pages 5269-5278Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200500268
Keywords
allenylzinc; chiral resolution; conformation analysis; diastereoselectivity; transition states
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In the presence of 60 equivalents of HMPA, the condensation of the racemic allenylzinc derived from 1-chloro-3-trimethylsilylpropyne onto enantiopure non-a-branched N-tert-butanesulfinimines was proven to give access to the corresponding cis-ethynylaziriclines as the major products. The good cis selectivity observed presumably resulted from a high kinetic resolution with the allenylzinc being partially configurationally labile with respect to the time scale defined by the rate of the reaction. Both single crystal X-ray analysis and semiempirical calculations conducted at the MM2 and AM1 levels of theory proved that the reaction certainly occurred through a preferred synclinal transition state in a supra- or antarafacial S,2' process. In all cases, chromatographic purification over silica gel allowed the cis-ethynyl-N-tertbutanesulfinylaziridines to be obtained as diastereo- and enantiomerically pure compounds (dr > 98:2 and ee > 99%).
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