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. 2012;84(8):1729-1739.
doi: 10.1351/PAC-CON-11-10-18. Epub 2012 Mar 13.

Formation of C-C bonds via ruthenium-catalyzed transfer hydrogenation()

Joseph Moran  1 , Michael J Krische
Affiliations

Formation of C-C bonds via ruthenium-catalyzed transfer hydrogenation()

Joseph Moran et al. Pure Appl Chem. 2012.

Abstract

Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C-C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed.

Keywords: C–C bond formation; catalysis; ruthenium catalysis; transfer hydrogenation.

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Figures

Scheme 1
Scheme 1
Ruthenium-catalyzed hydrohydroxyalkylation of 1,1-disubstituted allenes from the alcohol or aldehyde oxidation level. dippf = bis(diisopropylphosphino)ferrocene; NPthl = N-phthalimido.
Scheme 2
Scheme 2
Anti-diastereoselective ruthenium catalyzed hydrohydroxyalkylation of allenamides from the alcohol or aldehyde oxidation level. R1 = 4-nitrobenzenesulfonyl, R2 = 2,4-(MeO)2Bn.
Scheme 3
Scheme 3
Hydrohydroxyalkylation and hydroacylation of acyclic dienes from the alcohol or aldehyde oxidation level. aLigand = (p-MeOPh)3P, bLigand = rac-BINAP, cNo ligand added.
Scheme 4
Scheme 4
Hydrohydroxyalkylation of 2-substituted dienes to form all-carbon quaternary centers.
Scheme 5
Scheme 5
syn-Diastereo- and enantioselective carbonyl crotylation via hydrohydroxyalkylation of 2-silylbutadienes from the alcohol or aldehyde oxidation level. aChiral ligand = (R)-DM-SEGPHOS. bChiral ligand = (R)-SEGPHOS.
Scheme 6
Scheme 6
Coupling of alcohols with 2-butyne to provide products of alkyne hydrohydroxyalkylation or hydroacylation.
Scheme 7
Scheme 7
Hydrohydroxyalkylation of nonsymmetric internal alkynes from the aldehyde oxidation level.
Scheme 8
Scheme 8
Regiodivergence in ruthenium- and nickel-catalyzed reductive couplings of nonsymmetric disubstituted alkynes to paraformaldehyde.
Scheme 9
Scheme 9
Ruthenium-catalyzed hydrohydroxyalkylation of 1,3-enynes from the alcohol oxidation level. DPPF = 1,1'-bis(diphenylphosphino)ferrocene.
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References

    1. Frohning CD, Kohlpaintner CW. In: Applied Homogeneous Catalysis with Organometallic Compounds. Cornils B, Herrmann WA, editors. Vol. 1. Wiley-VCH; Weinheim: 1996. pp. 29–104.
    2. van Leeuwen PWNM. Homogeneous Catalysis: Understanding the Art. Kluwer; Dordrecht: 2004.

    1. For a review of ruthenium-catalyzed alkene hydroformylation, see: Kalck P, Peres Y, Jenck J. Adv. Organomet. Chem. 1991;32:121.

    1. For recent reviews on C–C bond-forming hydrogenation and transfer hydrogenation, see: Patman RL, Bower JF, Kim IS, Krische MJ. Aldrichim. Acta. 2008;41:95.Bower JF, Kim IS, Patman RL, Krische MJ. Angew. Chem., Int. Ed. 2009;48:34.Han SB, Kim IS, Krische MJ. Chem. Commun. 2009:7278.Bower JF, Krische MJ. Top. Organomet. Chem. 2011;43:107.

    1. In related “hydrogen auto-transfer” reactions, alcohol dehydrogenation and nucleophile generation occur independently. Hence, pre-activated nucleophiles are required. Such processes promote formal alcohol substitution rather than carbonyl addition. For selected reviews, see: Nixon TD, Whittlesey MK, Williams JMJ. Dalton Trans. 2009:753.Dobereiner GE, Crabtree RH. Chem. Rev. 2010;110:681.Guillena G, Ramón DJ, Yus M. Chem. Rev. 2010;110:1611.

    1. For a previous review on ruthenium-catalyzed transfer hydrogenative C–C bond formation, see: Shibahara F, Krische MJ. Chem. Lett. 2008;37:1102.

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