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. 2010 Oct 1;12(19):4348-51.
doi: 10.1021/ol101797f.

Ni(0)-catalyzed 1,4-selective diboration of conjugated dienes

Robert J Ely  1 , James P Morken
Affiliations

Ni(0)-catalyzed 1,4-selective diboration of conjugated dienes

Robert J Ely et al. Org Lett. .

Abstract

A catalytic stereoselective 1,4-diboration of conjugated dienes with B(2)(pin)(2) was accomplished with Ni(cod)(2) and PCy(3) as the catalyst. This reaction broadens the substrate scope of current methods for catalytic diene diboration by including internal and sterically hindered dienes, and it proceeds efficiently at low catalyst loadings. The intermediate allylboronate was oxidized to the stereodefined allylic 1,4-diol.

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Figures

Scheme 1
Scheme 1
Effect of Ligands on Ni-Catalyzed Diene Diboration
Scheme 2
Scheme 2
Comparison of the Diboration of Cis and Trans-1,3-Pentadiene
Scheme 3
Scheme 3
Large Scale Diboration of 1,3-Decadiene
Scheme 4
Scheme 4
Proposed Catalytic Cycle for Diene Diboration
See this image and copyright information in PMC

References

    1. For a review of Pt- and Rh-catalyzed diboration: Norman NC, Marder TB. Top. Catal. 1998;5:63. For Pd: Yang FY, Cheng H. J. Am. Chem. Soc. 2001;123:761. Woodward AR, Burks HE, Sieber JD, Morken JP. J. Am. Chem. Soc. 2004;126:16328. Lillo V, Mas-Marzá E, Segarra A, Carbó JJ, Bo C, Peris E, Fernandez E. Chem. Commun. 2007:3380. For Cu:Lillo V, Fructos MR, Braga AAC, Maseras F, Reguejo MM, Pérez PJ, Fernandez E. Chem.-Eur. J. 2007;13:2614. Lee Y, Jang H, Hoveyda AH. J. Am. Chem. Soc. 2009;131:16630. For Au: Baker RT, Nguyen P, Marder TB, Westcott SA. Angew. Chem. Int. Ed. 1995;34:1336. Corberan R, Ramirez J, Sanau M, Peris E, Fernandez E. Tetrahedron: Asymmetry. 2006;17:1759. Ramirez J, Sanau M, Fernandez E. Angew. Chem. Int. Ed. 2008;47:5194. For Ag: Corberan R, Ramirez J, Poyatos M, Peris E, Fernandez E. Chem. Commun. 2005:3056.

    1. Ishiyama T, Yamamoto M, Miyaura N. Chem. Commun. 1996:2073.
    2. Clegg W, Thorsten J, Marder TB, Norman NC, Orpen AG, Peakman TM, Quayle MJ, Rice CR, Scott AJ. J. Chem. Soc., Dalton Trans. 1998:1431.
    1. Burks HE, Kliman LT, Morken JP. J. Am. Chem. Soc. 2009;131:9134. - PMC - PubMed
    1. Cho HY, Morken JP. J Am. Chem. Soc. 2008;130:16140. - PMC - PubMed

    1. For an excellent description of the electronic properties of HMPT, see: Moloy KG, Petersen JL. J. Am. Chem. Soc. 1995;117:7696.

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