C O M M U N I C A T I O N S
Acknowledgment. This research was supported by the National
Institute of General Medical Sciences of the National Institutes of
Health (GM-54909). L.E.B. thanks the Department of Education
(GAANN) for a predoctoral fellowship. K.A.W. thanks Amgen and
Lilly for awards to support research. We thank Dr. W. S. Palmer
and Dr. Z. Neva´rez (UCI) for initial experiments. We thank Dr. P.
Dennison (UCI) for the assistance with NMR spectroscopy, Dr. J.
W. Ziller (UCI) for X-ray crystallography, and Dr. J. Greaves and
Ms. S. Sorooshian (UCI) for mass spectrometry.
Supporting Information Available: Experimental procedure,
spectroscopic, analytical, and X-ray data for the products (PDF, CIF).
This material is available free of charge via the Internet at http://
pubs.acs.org.
crystallography and analysis of chiral esters demonstrated that the
product was enantiomerically enriched, but it was a mixture of
enantiomeric silanes 12 and 12′.32 The observation of only cis
products indicates that formation of the new C-Si bond occurs
exclusively on the same face as the C-O bond that is broken. The
loss of enantiomeric purity shows that some, but not complete,
allylic transposition occurred. The retention of facial selectivity,
the evidence of some allylic transposition, and the intramolecularity
of the insertion are all consistent with a [1,2]-Stevens rearrangement
of an oxonium ylide.33-35 These observations, along with the lack
of allylic transposition in several cases (such as entries 1 and 3 of
Table 1), are inconsistent with a [2,3]-sila-Wittig reaction, which
would require retention of enantiopurity.36,37
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