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Compound 1 was isolated as a mixture of diastereomers (95/5). The identity of the major diastereomer is not known. Evidence (see ref 9) suggests that diastereoselectivity is largely sterically controlled. It is noteworthy that the diastereomeric ratio is inconsequential for the subsequent transformations of 1 in the applications described in this Letter.
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Eliel and Frye and co-workers have shown (see: Chen, X.; Hortelano, E. R.; Eliel, E. L.; Frye, S. V. J. Am. Chem. Soc. 1992, 114, 1778-1784) that the addition of Grignard reagents to α-siloxy ketones proceeds via chelated transition states to varying degrees. However, there is evidence that TES ethers can participate in chelatation to a significant extent. Due to competing steric effects of the bulky BOC-protected oxazolidine and the TES ether, it would be anticipated that an open transition state would afford low levels of diastereoselectivity. The lower diastereoselectivity at -10°C in comparison to that at -78°C can be attributed to the reaction proceeding through a mixture of chelated and open transition states with reaction through the chelated intermediate predominating to a greater extent at the lower temperature.
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