Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 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.

PubMed Disclaimer

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.
See this image and copyright information in PMC

References

    1. For selected reviews on C-C bond forming hydrogenation and transfer hydrogenation, see: Ngai MY, Kong JR, Krische MJ. J Org Chem. 2007;72:1063.Skucas E, Ngai MY, Komanduri V, Krische MJ. Acc Chem Res. 2007;40:1394.Shibahara F, Krische MJ. Chem Lett. 2008;37:1102.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.

    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.

Publication types