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. 2005 May 4;127(17):6170-1.
doi: 10.1021/ja043884l.

Three-component coupling reactions of silylglyoxylates, alkynes, and aldehydes: a chemoselective one-step glycolate aldol construction

David A Nicewicz  1 , Jeffrey S Johnson
Affiliations

Three-component coupling reactions of silylglyoxylates, alkynes, and aldehydes: a chemoselective one-step glycolate aldol construction

David A Nicewicz et al. J Am Chem Soc. .

Abstract

A single-pot three-component coupling reaction of silylglyoxylates (1), terminal alkynes, and aldehydes in the presence of ZnI2 and Et3N is presented. The products of the reaction, densely functionalized silyl-protected glycolate aldols (2), can be converted to the corresponding acetonides (3) in a one-pot deprotection/ketalization sequence. A variety of terminal alkynes and aldehydes can be successfully employed to give a range of highly functionalized, fully protected 1,2-diols in good yields and moderate diastereoselectivities. Mechanistic experiments suggest that the zinc acetylide reacts with the silylgyloxylate (1) in a chemoselective manner. Using an unoptimized (+)-N-methylephedrine and Zn(OTf)2 system, silyl-deprotected adduct 2 was formed in 64% ee and 89:11 dr.

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Figures

Scheme 1
Scheme 1
Scheme 2
Scheme 2
Mechanistic Study
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References

    1. Moser WH. Tetrahedron. 2001;57:2065.
    1. Brook AG. Acc Chem Res. 1974;7:77.
    1. Reich HJ, Holtan RC, Bolm C. J Am Chem Soc. 1990;112:5609.
    2. Takeda K, Ohnishi Y. Tetrahedron Lett. 2000;41:4169.
    3. Degl’Innocenti A, Ricci A, Mordini A, Reginato G, Colotta V. Gazz Chim Ital. 1987;117:645.
    1. Nicewicz DA, Yates CM, Johnson JS. Angew Chem, Int Ed. 2004;43:2652. - PubMed
    2. Linghu X, Nicewicz DA, Johnson JS. Org Lett. 2002;4:2957. - PubMed
    3. Linghu X, Johnson JS. Angew Chem, Int Ed. 2003;42:2534. - PubMed
    1. Takeda K, Tanaka T. Synlett. 1999:705.

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