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. 2009 Aug 19;131(32):11332-4.
doi: 10.1021/ja904504j.

Enantioselective aldehyde alpha-nitroalkylation via oxidative organocatalysis

Jonathan E Wilson  1 , Anthony D Casarez, David W C MacMillan
Affiliations

Enantioselective aldehyde alpha-nitroalkylation via oxidative organocatalysis

Jonathan E Wilson et al. J Am Chem Soc. .

Abstract

The first enantioselective organocatalytic alpha-nitroalkylation of aldehydes has been accomplished. The aforementioned process involves the oxidative coupling of an enamine intermediate, generated transiently via condensation of an amine catalyst with an aldehyde, with a silyl nitronate to produce a beta-nitroaldehyde. Two methods, one that furnishes the syn beta-nitroaldehyde and a second that provides access to the anti isomer, have been developed. Data are presented to support a hypothesis that explains this phenomenon in terms of a silyl group-controlled change in mechanism. Finally, a three-step procedure for the synthesis of both syn- and anti-alpha,beta-disubstituted beta-amino acids is presented.

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Figures

Figure 1
Figure 1
Structural Similarity of SOMO and Enamine Intermediate.
Scheme 1
Scheme 1
Possible Mechanistic Scenarios for Nitroalkylation.
Scheme 2
Scheme 2
Three-Step Diastereoselective β-Amino Acid Synthesis.
Scheme 3
Scheme 3
Proposed Divergence of Mechanistic Pathways.
Scheme 4
Scheme 4
Distinguishing Divergent Mechanistic Pathways.
See this image and copyright information in PMC

References

    1. Juriasti E, Soloshonok VA, editors. Enantioselective Synthesis of β-Amino Acids. 2nd Ed. Hoboken NJ: John Wiley & Sons; 2005.

    1. Yang JW, Stadler M, List B. Angew. Chem. Int. Ed. 2007;46 609 and ref cited therein. (b) For a review on organocatalytic approaches, see: Ting A, Schaus SE. Eur. J. Org. Chem. 2007:5797.

    1. Genet J-P. In: Modern Reduction Methods. Andersson PG, Munslow IJ, editors. Weinheim: Wiley-VCH; 2008. p. 3.
    1. Sibi MP, Prabagaran N, Ghorpade SP, Jasperse SP. J. Am. Chem. Soc. 2003;125:11796. - PubMed
    2. Chen YK, Yoshida M, MacMillan DWC. J. Am. Chem. Soc. 2006;128:9328. - PubMed
    1. Hodous BL, Fu GC. J. Am. Chem. Soc. 2001;124:1578. - PubMed
    2. Taggi AE, Hafez AM, Wack H, Young B, Ferraris D, Leckta T. J. Am. Chem. Soc. 2002;124:6626. - PubMed
    3. Lee EC, Hodous BL, Bergin E, Shih C, Fu GC. J. Am. Chem. Soc. 2005;127:11586. - PubMed

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