Abstract
Enzymes are a continuing source of inspiration for the design of new chemical reactions that proceed with efficiency, high selectivity and minimal waste. In many biochemical processes, different catalytic species, such as Lewis acids and bases, are involved in precisely orchestrated interactions to activate reactants simultaneously or sequentially. This type of ‘cooperative catalysis’, in which two or more catalytic cycles operate concurrently to achieve one overall transformation, has great potential in enhancing known reactivity and driving the development of new chemical reactions with high value. In this disclosure, a cooperative N-heterocyclic carbene/Lewis acid catalytic system promotes the addition of homoenolate equivalents to hydrazones, generating highly substituted γ-lactams in moderate to good yields and with high levels of diastereo- and enantioselectivity.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Kanai, M., Kato, N., Ichikawa, E. & Shibasaki, M. Power of cooperativity: Lewis acid–Lewis base bifunctional asymmetric catalysis. Synlett 1491–1508 (2005).
Breslow, R. Bifunctional acid–base catalysis by imidazole groups in enzyme mimics. J. Mol. Catal. 91, 161–174 (1994).
Breslow, R. Bifunctional binding and catalysis. Supramol. Chem. 1, 111–118 (1993).
Lee, J. K., Kung, M. C. & Kung, H. H. Cooperative catalysis: a new development in heterogeneous catalysis. Top. Catal. 49, 136–144 (2008).
Miyabe, H. & Takemoto, Y. Discovery and application of asymmetric reaction by multi-functional thioureas. Bull. Chem. Soc. Jpn 81, 785–795 (2008).
Paull, D. H., Abraham, C. J., Scerba, M. T., Alden-Danforth, E. & Lectka, T. Bifunctional asymmetric catalysis: cooperative Lewis acid/base systems. Acc. Chem. Res. 41, 655–663 (2008).
Frank, R. A. W., Titman, C. M., Pratap, J. V., Luisi, B. F. & Perham, R. N. A molecular switch and proton wire synchronize the active sites in thiamine enzymes. Science 306, 872–876 (2004).
Jordan, F. & Patel, M. S. Thiamine: Catalytic Mechanisms in Normal and Disease States (Marcel Dekker, 2004).
Denmark, S. E. & Beutner, G. L. Lewis base catalysis in organic synthesis. Angew. Chem. Int. Ed. 47, 1560–1638 (2008).
Enders, D., Niemeier, O. & Henseler, A. Organocatalysis by N-heterocyclic carbenes. Chem. Rev. 107, 5606–5655 (2007).
Phillips, E. M., Chan, A. & Scheidt, K. A. Discovering new reactions with N-heterocyclic carbenes. Aldrichimica Acta 42, 55–66 (2009).
Sheehan, J. C. & Hara, T. Asymmetric thiazolium salt catalysis of the benzoin condensation. J. Org. Chem. 39, 1196–1199 (1974).
Stetter, H., Raemsch, R. Y. & Kuhlmann, H. The preparative use of thiazolium salt-catalyzed acyloin and benzoin formation, i. Preparation of simple acyloins and benzoins. Synthesis 733–735 (1976).
Breslow, R. & Schmuck, C. The mechanism of thiazolium catalysis. Tetrahedron Lett. 37, 8241–8242 (1996).
Enders, D. & Kallfass, U. An efficient nucleophilic carbene catalyst for the asymmetric benzoin condensation. Angew. Chem. Int. Ed. 41, 1743–1745 (2002).
Kerr, M. S., de Alaniz, J. R. & Rovis, T. A highly enantioselective catalytic intramolecular Stetter reaction. J. Am. Chem. Soc. 124, 10298–10299 (2002).
Mattson, A. E., Bharadwaj, A. R. & Scheidt, K. A. The thiazolium-catalyzed sila-Stetter reaction: conjugate addition of acylsilanes to unsaturated esters and ketones. J. Am. Chem. Soc. 126, 2314–2315 (2004).
Burstein, C. & Glorius, F. Organocatalyzed conjugate umpolung of α,β-unsaturated aldehydes for the synthesis of γ-butyrolactones. Angew. Chem. Int. Ed. 43, 6205–6208 (2004).
Chan, A. & Scheidt, K. A. Conversion of α,β-unsaturated aldehydes into saturated esters: an umpolung reaction catalyzed by nucleophilic carbenes. Org. Lett. 7, 905–908 (2005).
Sohn, S. S., Rosen, E. L. & Bode, J. W. N-heterocyclic carbene-catalyzed generation of homoenolates: γ-butyrolactones by direct annulations of enals and aldehydes. J. Am. Chem. Soc. 126, 14370–14371 (2004).
Nair, V., Vellalath, S., Poonoth, M. & Suresh, E. N-heterocyclic carbene-catalyzed reaction of chalcones and enals via homoenolate: an efficient synthesis of 1,3,4-trisubstituted cyclopentenes. J. Am. Chem. Soc. 128, 8736–8737 (2006).
Chan, A. & Scheidt, K. A. Highly stereoselective formal [3 + 3] cycloaddition of enals and azomethine imines catalyzed by N-heterocyclic carbenes. J. Am. Chem. Soc. 129, 5334–5335 (2007).
Phillips, E. M., Reynolds, T. E. & Scheidt, K. A. Highly diastereo- and enantioselective additions of homoenolates to nitrones catalyzed by N-heterocyclic carbenes. J. Am. Chem. Soc. 130, 2416–2417 (2008).
Phillips, E. M., Wadamoto, M., Chan, A. & Scheidt, K. A. A highly enantioselective intramolecular Michael reaction catalyzed by N-heterocyclic carbenes. Angew. Chem. Int. Ed. 46, 3107–3110 (2007).
Wadamoto, M., Phillips, E. M., Reynolds, T. E. & Scheidt, K. A. Enantioselective synthesis of α,α-disubstituted cyclopentenes by an N-heterocyclic carbene-catalyzed desymmetrization of 1,3-diketones. J. Am. Chem. Soc. 129, 10098–10099 (2007).
Reynolds, T. E., Stern, C. A. & Scheidt, K. A. N-heterocyclic carbene-initiated alpha-acylvinyl anion reactivity: Additions of alpha-hydroxypropargylsilanes to aldehydes. Org. Lett. 9, 2581–2584 (2007).
Burgess, K. & Perry, M. C. Chiral N-heterocyclic carbene–transition metal complexes in asymmetric catalysis. Tetrahedron: Asymmetry 14, 951–961 (2003).
Brown, M. K., May, T. L., Baxter, C. A. & Hoveyda, A. H. All-carbon quaternary stereogenic centers by enantioselective Cu-catalyzed conjugate additions promoted by a chiral N-heterocyclic carbene. Angew. Chem. Int. Ed. 46, 1097–1100 (2007).
Lee, Y., Li, B. & Hoveyda, A. H. Stereogenic-at-metal Zn- and Al-based N-heterocyclic carbene (NHC) complexes as bifunctional catalysts in Cu-free enantioselective allylic alkylations. J. Am. Chem. Soc. 131, 11625–11633 (2009).
Nolan, S. P. N-Heterocyclic Carbenes in Synthesis (Wiley-VCH, 2006).
Diez-Gonzalez, S., Marion, N. & Nolan, S. P. N-heterocyclic carbenes in late transition metal catalysis. Chem. Rev. 109, 3612–3676 (2009).
Lin, J. C. Y. et al. Coinage metal-N-heterocyclic carbene complexes. Chem. Rev. 109, 3561–3598 (2009).
Glorius, F. E. N-Heterocyclic Carbenes in Transition Metal Catalysis (Springer-Verlag, 2007).
Lebeuf, R., Hirano, K. & Glorius, F. Palladium-catalyzed C-allylation of benzoins and an NHC-catalyzed three component coupling derived thereof: compatibility of NHC- and Pd-catalysts. Org. Lett. 10, 4243–4246 (2008).
Tran, J. A. et al. Design and synthesis of 3-arylpyrrolidine-2-carboxamide derivatives as melanocortin-4 receptor ligands. Bioorg. Med. Chem. Lett. 18, 1931–1938 (2008).
Silverman, R. B. & Nanavati, S. M. Selective-inhibition of gamma-aminobutyric-acid aminotransferase by (3R,4R),(3S,4S)-4-amino-5-fluoro-3-phenylpentanoic and (3R,4S),(3S,4R)-4-amino-5-fluoro-3-phenylpentanoic acids. J. Med. Chem. 33, 931–936 (1990).
Hartwig, W. & Born, L. Diastereoselective and enantioselective total synthesis of the hepatoprotective agent clausenamide. J. Org. Chem. 52, 4352–4358 (1987).
He, M. & Bode, J. W. Catalytic synthesis of gamma-lactams via direct annulations of enals and N-sulfonylimines. Org. Lett. 7, 3131–3134 (2005).
Sugiura, M. & Kobayashi, S. N-acylhydrazones as versatile electrophiles for the synthesis of nitrogen-containing compounds. Angew. Chem. Int. Ed. 44, 5176–5186 (2005).
Kaljurand, I. et al. Extension of the self-consistent spectrophotometric basicity scale in acetonitrile to a full span of 28 pk(a) units: unification of different basicity scales. J. Org. Chem. 70, 1019–1028 (2005).
Beach, R. G. & Ashby, E. C. Synthesis and characterization of dialkyl(aryl)aminomagnesium hydrides and alkoxy(aryloxy)magnesium hydrides. Inorg. Chem. 10, 906–910 (1971).
Stephan, D. W. & Erker, G. Frustrated Lewis pairs: metal-free hydrogen activation and more. Angew. Chem. Int. Ed. 49, 46–76 (2010).
Tang, K. & Zhang, J. T. The effects of (–)clausenamide on functional recovery in transient focal cerebral ischemia. Neurol. Res. 24, 473–478 (2002).
Haldar, P. & Ray, J. K. Chemoselective reduction of a lactam carbonyl group in the presence of a gem-dicarboxylate by sodium borohydride and iodine: a facile entry to N-aryl trisubstituted pyrroles. Tetrahedron Lett. 44, 8229–8231 (2003).
Arnold, U. et al. Protein prosthesis: a nonnatural residue accelerates folding and increases stability. J. Am. Chem. Soc. 125, 7500–7501 (2003).
Mukherjee, S., Yang, J. W., Hoffmann, S. & List, B. Asymmetric enamine catalysis. Chem. Rev. 107, 5471–5569 (2007).
MacMillan, D. W. C. The advent and development of organocatalysis. Nature 455, 304–308 (2008).
Acknowledgements
Support for this work was generously provided by National Institute of General Medical Sciences (RO1 GM73072), GlaxoSmithKline, AstraZeneca and the Alfred P. Sloan Foundation. B.C.D. thanks the Fonds Quebecois de la Recherche sur la Nature et les Technologies for a postdoctoral fellowship. Funding for the Northwestern University Integrated Molecular Structure Education and Research Center (IMSERC) has been furnished in part by the National Science Foundation (CHE-9871268). T. Reynolds and J. Roberts provided X-ray crystallography support.
Author information
Authors and Affiliations
Contributions
K.A.S. conceived the idea and wrote the manuscript. D.E.A.R., B.C.-D. and D.H. performed the experiments. All the authors analysed the data. K.A.S., D.E.A.R. and B.C.-D contributed to discussions and edited the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 1940 kb)
Supplementary information
Crystallographic data for compound 3fa (CIF 12 kb)
Rights and permissions
About this article
Cite this article
Raup, D., Cardinal-David, B., Holte, D. et al. Cooperative catalysis by carbenes and Lewis acids in a highly stereoselective route to γ-lactams. Nature Chem 2, 766–771 (2010). https://doi.org/10.1038/nchem.727
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nchem.727
This article is cited by
-
N-Heterocyclic carbene-catalyzed enantioselective (dynamic) kinetic resolutions and desymmetrizations
Science China Chemistry (2024)
-
Carbene-catalyzed enantioselective seleno-Michael addition as access to antimicrobial active Se-containing heterocycles
Science China Chemistry (2024)
-
Green Acetylation of Primary Aromatic Amines
Resonance (2023)
-
Bifunctional reagents in organic synthesis
Nature Reviews Chemistry (2021)
-
Recent advances in the chemistry and applications of N-heterocyclic carbenes
Nature Reviews Chemistry (2021)