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. 2012 Apr 18;134(15):6556-9.
doi: 10.1021/ja301640e. Epub 2012 Mar 30.

Asymmetric hydrovinylation of 1-vinylcycloalkenes. Reagent control of regio- and stereoselectivity

Jordan P Page  1 , T V RajanBabu
Affiliations

Asymmetric hydrovinylation of 1-vinylcycloalkenes. Reagent control of regio- and stereoselectivity

Jordan P Page et al. J Am Chem Soc. .

Abstract

1-Vinylcycloalkenes undergo highly regio- and enantioselective (>98% ee) 1,4-hydrovinylation (HV) when treated with ethylene (1 atm) at room temperature in the presence of [(S,S)-2,4-bis-diphenylphosphinopentane (BDPP)]CoCl(2) (0.05 equiv) and methylaluminoxane. The minor 1,2-HV products, seen only in 1-vinylcyclohexene (~15%) and 1-vinylcycloheptene (2%), are formed as racemic mixtures. The corresponding Ni(II)-catalyzed HV reactions of these substrates give mostly the 1,2-adducts. Racemic 4-tert-butyl-1-vinylcyclohexene, when treated with Co[(S,S)-(BDPP)]Cl(2) and ethylene, undergoes a rare enantiodivergent reaction giving two diastereomers each in >98% ee.

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Figures

Scheme 1
Scheme 1
1,2- vs 1,4-Hydrovinylation of 4-t-Butyl-1-vinylcyclohexene
See this image and copyright information in PMC

References

    1. Zhang A, RajanBabu TV. J. Am. Chem. Soc. 2006;128:54. - PubMed
    2. Mans DJ, Cox GA, RajanBabu TV. J. Am. Chem. Soc. 2011;133:5776. - PMC - PubMed
    3. RajanBabu TV. Synlett. 2009;853 - PMC - PubMed
    1. Saha B, Smith CR, RajanBabu TV. J. Am. Chem. Soc. 2008;130:9000. - PMC - PubMed

    1. Sharma RK, RajanBabu TV. J. Am. Chem. Soc. 2010;132:3295. Other reports of Co-catalyzed asymmetric hydrovinylation: Grutters MMP, Müller C, Vogt D. J. Am. Chem. Soc. 2006;128:7414. Grutters MMP, van der Vlugt JI, Pei Y, Mills AM, Lutz M, Spek AL, Müller C, Moberg C, Vogt D. Adv. Synth. Catal. 2009;351:2199.

    1. Co(I)-catalyzed hydroalkenylation of dienes has attracted significant attention in the past decade, primarily due the seminal studies of the Hilt group. For a recent review, see: Hilt G. Synlett. 2011;1654 For representative examples of hydroalkenylation of dienes, see: Hilt G, du Mesnil F-X, Lüers S. Angew. Chem. Int. Ed. 2001;40:387. Hilt G, Lüers S. Synthesis. 2002;609 Hilt G, Danz M, Treutwein J. Org. Lett. 2009;11:3322. Arndt M, Reinhold A, Hilt G. J. Org. Chem. 2010;75:5203. Hilt G, Roesner S. Synthesis. 2011;662 Bohn MA, Schmidt A, Hilt G, Dindaroglu M, Schmalz H-G. Angew. Chem. Int. Ed. 2011;50:9689. For related Fe-catalyzed reactions, see: Ehlers J, König WA, Lutz S, Wenz G, tom Dieck H. Angew. Chem. Int. Ed. Engl. 1988;27:1556. Moreau B, Wu JY, Ritter T. Org. Lett. 2009;11:337. Control of regioselectivity is a particularly important aspect of coupling reactions of 1,3-dienes. For a noteworthy application of ligand control of regioselectivity in the context of the Co(I)-chemistry, see: Arndt M, Dindaroglu M, Schmalz H-G, Hilt G. Org. Lett. 2011;13:6236. and references cited therein.

    1. Ligands: BDPP = 2,4-diphenylphosphinopentane; DPPM = diphenylphosphinomethane; DPPE = diphenylphosphinoethane; DPPP = diphenylphosphinopropane; DPPB = diphenylphophinobutane; Cy3P = tricyclohexylphosphine; DIOP = (2,2-dimethyl-1,3-dioxalane-4,5-diylbismethylene) bis-diphenylphosphine.

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