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. 2010 Jun 4;12(11):2514-6.
doi: 10.1021/ol1007235.

Allenamide hydro-hydroxyalkylation: 1,2-amino alcohols via ruthenium-catalyzed carbonyl anti-aminoallylation

Jason R Zbieg  1 , Emma L McInturff, Michael J Krische
Affiliations

Allenamide hydro-hydroxyalkylation: 1,2-amino alcohols via ruthenium-catalyzed carbonyl anti-aminoallylation

Jason R Zbieg et al. Org Lett. .

Abstract

Exposure of alcohols to allenamides in the presence of RuHCl(CO)(PPh(3))(3) and dippf [dippf = bis(diisopropylphosphino)ferrocene] results in hydrogen transfer to generate aldehyde-allylruthenium pairs, which engage in C-C coupling to form products of carbonyl aminoallylation as single anti-diastereomers.

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Figures

Scheme 1
Scheme 1
anti-Diastereoselective coupling of allenamide 1a to alcohols 2a-2l to provide anti-aminoalcohols 3a-3l.a aAll reactions were performed in 13 x 100 mm pressure tubes. The cited yields are of material isolated by silica gel chromatography. Diastereoselectivities were determined by 1H NMR analysis of crude reaction mixtures. In each case, >20:1 anti-diastereoselectivity was observed. bThree equivalents of 1a were used. See Supporting Information for experimental details.
Scheme 2
Scheme 2
Catalytic C-C coupling of 1,1-disubstituted allene 1b to alcohols 2d and 2g.a aAs described in Table 2. See Supporting Information for experimental details.
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References

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    1. For related “hydrogen auto-transfer” reactions, alcohol dehydrogenation and nucleophile generation occur independently. Hence, conventional pre-activated nucleophiles are required. Such processes deliver products of formal alcohol substitution rather than carbonyl addition. For selected reviews, see: Guillena G, Ramón DJ, Yus M. Angew Chem Int Ed. 2007;46:2358.Hamid MHSA, Slatford PA, Williams JMJ. Adv Synth Catal. 2007;349:1555.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.Related dehydrogenative couplings of amines also require pre-activated nucleophiles, see: Li CJ. Acc Chem Res. 2009;42:335.

    1. For ruthenium catalyzed transfer hydrogenative coupling of alcohols to dienes, see: Shibahara F, Bower JF, Krische MJ. J Am Chem Soc. 2008;130:6338.Shibahara F, Bower JF, Krische MJ. J Am Chem Soc. 2008;130:14120.Smejkal T, Han H, Breit B, Krische MJ. J Am Chem Soc. 2009;131:10366.

    1. For ruthenium catalyzed transfer hydrogenative coupling of alcohols to enynes, see: Patman RL, Williams VM, Bower JF, Krische MJ. Angew Chem Int Ed. 2008;47:5220.

    1. For ruthenium catalyzed transfer hydrogenative coupling of alcohols to alkynes, see: Patman RL, Chaulagain MR, Williams VM, Krische MJ. J Am Chem Soc. 2009;131:2066.Williams VM, Leung JC, Patman RL, Krische MJ. Tetrahedron. 2009;65:5024.

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