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. 2009 Jul 8;131(26):9134-5.
doi: 10.1021/ja809610h.

Asymmetric 1,4-dihydroxylation of 1,3-dienes by catalytic enantioselective diboration

Heather E Burks  1 , Laura T Kliman, James P Morken
Affiliations

Asymmetric 1,4-dihydroxylation of 1,3-dienes by catalytic enantioselective diboration

Heather E Burks et al. J Am Chem Soc. .

Erratum in

  • J Am Chem Soc. 2010 Oct 6;132(39):13949

Abstract

Asymmetric 1,4-dihydroxylations of 1,3-dienes, and other transformations, are initiated by the Pt-catalyzed enantioselective addition of bis(pinacolato)diboron (B(2)(pin)(2)) to conjugated dienes. The studies reported in this communication suggest that both cyclic and acyclic substrates will participate in this reaction; however, dienes which are unable to adopt the S-cis conformation are unreactive. For most substrates, 1,4-addition is the predominant pathway. In addition to oxidation to the derived 2-buten-1,4-diol, stereoselective carbonyl allylation with the intermediate bis(boronate) ester is also described.

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Figures

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Scheme 4
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References

    1. For recent applications of the singlet oxygen [4+2] cycloaddition in synthesis, see:Lee JS, Fuchs PL. J. Am. Chem. Soc. 2005;127:13122.Barbarow JE, Miller AK, Trauner D. Org. Lett. 2005;7:2901.Ono K, Nakagawa M, Nishida A. Angew. Chem. Int. Ed. 2004;43:2020.Kusama H, Hara R, Kawahara S, Nishimori T, Kashima H, Nakamura N, Morihira K, Kuwajima I. J. Am. Chem. Soc. 2000;122:3811.Zhou G, Gao X, Li WZ, Li Y. Tetrahedron Lett. 2001;42:3101.Izzo I, Meduri G, Avallone E, De Riccardis F, Sodano G. Eur. J. Org. Chem. 2000:439.For recent reviews, see:Clennan EL, Pace A. Tetrahedron. 2005;61:6665.

    1. For the enantioselective desymmetrization of 1O2 cycloadducts, see: Staben ST, Xin L, Toste FD. J. Am. Chem. Soc. 2006;128:12658.

    1. For a recent review of this process: Bäckvall J-E. Palladium-Catalyzed 1,4-Additions to Conjugated Dienes. In: De Meijere A, Diederich F, editors. Metal Catalyzed Cross-Coupling Reactions. 2nd Edition Weinheim; Wiley-VCH: 2004. pp. 479–529.

    1. Thorarensen A, Palmgren A, Itami K, Bäckvall J-E. Tetrahedron Lett. 1997;38:8541.
    2. Itami K, Palmgren A, Thorarensen A, Bäckvall J-E. J. Org. Chem. 1998;63:6466.
    3. Verboom RC, Plietker BJ, Bäckvall J-E. J. Organomet. Chem. 2003;687:508.
    4. El-Qisairi AK, Qaseer HA, Fennelly JP, Chiarelli MP, Henry PM. Catalysis Commun. 2008;9:1661.

    1. Recent reviews: Burks HE, Morken JP. Chem. Commun. 2007:4717.Ramirez J, Lillo V, Segarra AM, Fernandez E. Comp. Rend. Chim. 2007;10:138.Beletskaya I, Moberg C. Chem. Rev. 2006;106:2320.Ishiyama T, Miyaura N. Chem. Record. 2004;3:271.

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