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. 2010 Apr 21;132(15):5354-6.
doi: 10.1021/ja101076q.

Super silyl stereo-directing groups for complete 1,5-syn and -anti stereoselectivities in the aldol reactions of beta-siloxy methyl ketones with aldehydes

Yousuke Yamaoka  1 , Hisashi Yamamoto
Affiliations

Super silyl stereo-directing groups for complete 1,5-syn and -anti stereoselectivities in the aldol reactions of beta-siloxy methyl ketones with aldehydes

Yousuke Yamaoka et al. J Am Chem Soc. .

Abstract

In this communication, we report that substrate-controlled 1,5-syn and -anti stereoinduction in the aldol reaction of beta-tris(trialkylsilyl)siloxy methyl ketones can be achieved with high diastereoselectivities. Tris(trialkylsilyl)silyl groups are easily prepared and play an important role in the selectivities of these reactions. Furthermore, all of the 1,3,5-triol stereoisomers can easily be prepared from beta-siloxy methyl ketones in no more than three steps.

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Figures

Figure 1
Figure 1
Plausible transition-states for 1,5-syn and 1,5-anti inductions.
Scheme 1
Scheme 1
Aldol reactions utilizing 1,3- and 1,5-stereoinduction.
Scheme 2
Scheme 2
Syntheses of 1,3,5-triols.
Scheme 3
Scheme 3
Double stereodifferentiating aldol reactions.
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