Abstract
Despite the tremendous advances of the past four decades, chemists are far from being able to use chiral catalysts to control the stereoselectivity of any desired reaction. New concepts for the construction and mode of operation of chiral catalysts have the potential to open up previously inaccessible reaction space. The recognition and categorization of distinct approaches seems to play a role in triggering rapid exploration of new territory. This Review both reflects on the origins as well as details a selection of the latest examples of an area that has advanced considerably within the past five years or so: the use of chiral anions in asymmetric catalysis. Defining reactions as involving chiral anions is a difficult task owing to uncertainties over the exact catalytic mechanisms. Nevertheless, we attempt to provide an overview of the breadth of reactions that could reasonably fall under this umbrella.
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References
Walsh, P. J. & Kozlowski, M. C. Fundamentals of Asymmetric Catalysis (University Science Books, 2008).
Yamamoto, H. Lewis Acids in Organic Synthesis (Wiley-VCH, 2000).
Akiyama, T. Stronger Brønsted acids. Chem. Rev. 107, 5744–5758 (2007).
Jakab, G., Tancon, C., Zhang, Z., Lippert, K. M. & Schreiner, P. R. (Thio)urea organocatalyst equilibrium acidities in DMSO. Org. Lett. 14, 1724–1727 (2012).
Taylor, M. S. & Jacobsen, E. N. Asymmetric catalysis by chiral hydrogen-bond donors. Angew. Chem. Int. Ed. 45, 1520–1543 (2006).
Vachal, P. & Jacobsen, E. N. Structure-based analysis and optimization of a highly enantioselective catalyst for the Strecker reaction. J. Am. Chem. Soc. 124, 10012–10014 (2002).
Huang, Y., Unni, A. K., Thadani, A. N. & Rawal, V. H. Hydrogen bonding: Single enantiomers from a chiral-alcohol catalyst. Nature 424, 146–146 (2003).
Doyle, A. G. & Jacobsen, E. N. Small-molecule H-bond donors in asymmetric catalysis. Chem. Rev. 107, 5713–5743 (2007).
Christ, P. et al. pKa values of chiral Brønsted acid catalysts: phosphoric acids/amides, sulfonyl/sulfuryl imides, and perfluorinated TADDOLs (TEFDDOLs). Chem. Eur. J. 17, 8524–8528 (2011).
Terada, M. Chiral phosphoric acids as versatile catalysts for enantioselective transformations. Synthesis 1929–1982 (2010).
Simón, L. & Goodman, J. M. A model for the enantioselectivity of imine reactions catalyzed by BINOL-phosphoric acid catalysts. J. Org. Chem. 76, 1775–1788 (2011).
Hatano, M., Maki, T., Moriyama, K., Arinobe, M. & Ishihara, K. Pyridinium 1,1′-binaphthyl-2,2′ disulfonates as highly effective chiral brønsted acid−base combined salt catalysts for enantioselective Mannich-type reaction. J. Am. Chem. Soc. 130, 16858–16860 (2008).
Simón, L. & Goodman, J. M. Theoretical study of the mechanism of Hantzsch ester hydrogenation of imines catalyzed by chiral BINOL-phosphoric acids. J. Am. Chem. Soc. 130, 8741–8747 (2008).
Fleischmann, M., Drettwan, D., Sugiono, E., Rueping, M. & Gschwind, R. M. Brønsted acid catalysis: hydrogen bonding versus ion pairing in imine activation. Angew. Chem. Int. Ed. 50, 6364–6369 (2011).
Lacour, J. & Hebbe-Viton, V. Recent developments in chiral anion mediated asymmetric chemistry. Chem. Soc. Rev. 32, 373–382 (2003).
Lacour, J. & Moraleda, D. Chiral anion-mediated asymmetric ion pairing chemistry. Chem. Commun. 7073–7089 (2009).
Shao, Z. & Zhang, H. Combining transition metal catalysis and organocatalysis: a broad new concept for catalysis. Chem. Soc. Rev. 38, 2745–2755 (2009).
Zhong, C. & Shi, X. When organocatalysis meets transition-metal catalysis. Eur. J. Org. Chem. 2010, 2999–3025 (2010).
Rueping, M., Koenigs, R. M. & Atodiresei, I. Unifying metal and Brønsted acid catalysis—concepts, mechanisms, and classifications. Chem. Eur. J. 16, 9350–9365 (2010).
Eliel, E. L., Mander, L. N. & Wilen, S. H. Stereochemistry of Organic Compounds (Wiley-Interscience, 1994)
Jacques, J., Fouquey, C. & Viterbo, R. Enantiomeric cyclic binaphthyl phosphoric acids as resolving agents. Tetrahedron Lett. 12, 4617–4620 (1971).
Lacour, J., Ginglinger, C., Grivet, C. & Bernardinelli, G. Synthesis and resolution of the configurationally stable tris(tetrachlorobenzenediolato)phosphate(v) ion. Angew. Chem. Int. Ed. 36, 608–610 (1997).
Lacour, J., Ginglinger, C. & Favarger, F. Asymmetric recognition of TRISPHAT anion. Unusually high difference in reactivity of the pseudoenantiomers of cinchona alkaloids. Tetrahedron Lett. 39, 4825–4828 (1998).
Shevchenko, I. V., Fischer, A., Jones, P. G. & Schmutzler, R. The unusual oxidation of a 1,5,2,4-diazadiphosphorinan-6-one with tetrachloro-ortho-benzoquinone. Chem. Ber. 125, 1325–1332 (1992).
Ishihara, K., Miyata, M., Hattori, K., Tada, T. & Yamamoto, H. A New chiral BLA promoter for asymmetric aza Diels–Alder and aldol-type reactions of imines. J. Am. Chem. Soc. 116, 10520–10524 (1994).
Maruoka, K. Asymmetric Phase Transfer Catalysis (Wiley-VCH, 2008).
Ojima, I. Catalytic Asymmetric Synthesis (Wiley-VCH, 2000).
Maruoka, K. & Ooi, T. Enantioselective amino acid synthesis by chiral phase-transfer catalysis. Chem. Rev. 103, 3013–3028 (2003).
Lygo, B. & Andrews, B. I. Asymmetric phase-transfer catalysis utilizing chiral quaternary ammonium salts: asymmetric alkylation of glycine imines. Acc. Chem. Res. 37, 518–525 (2004).
O'Donnell, M. J. The enantioselective synthesis of alpha-amino acids by phase-transfer catalysis with achiral Schiff base esters. Acc. Chem. Res. 37, 506–517 (2004).
Ooi, T. & Maruoka, K. Recent advances in asymmetric phase-transfer catalysis. Angew. Chem. Int. Ed. 46, 4222–4266 (2007).
Dolling, U. H., Davis, P. & Grabowski, E. J. J. Efficient catalytic asymmetric alkylations. 1. Enantioselective synthesis of (+)-indacrinone via chiral phase-transfer catalysis. J. Am. Chem. Soc. 106, 446–447 (1984).
Hughes, D. L., Dolling, U. H., Ryan, K. M., Schoenewaldt, E. F. & Grabowski, E. J. J. Efficient catalytic asymmetric alkylations. 3. A kinetic and mechanistic study of the enantioselective phase-transfer methylation of 6,7-dichloro-5-methoxy-2-phenyl-1-indanone. J. Org. Chem. 52, 4745–4752 (1987).
O'Donnell, M. J., Delgado, F., Hostettler, C. & Schwesinger, R. An efficient homogeneous catalytic enantioselective synthesis of α-amino acid derivatives. Tetrahedron Lett. 39, 8775–8778 (1998).
Owen, D. J. & Schuster, G. B. Induced circular dichroism in cyanine borate penetrated ion pairs. J. Am. Chem. Soc. 118, 259–260 (1996).
Lacour, J., Jodry, J. J., Ginglinger, C. & Torche-Haldimann, S. Diastereoselective ion pairing of TRISPHAT anions and tris(4,4′-dimethyl-2,2′-bipyridine)iron(II). Angew. Chem. Int. Ed. 37, 2379–2380 (1998).
Llewellyn, D. B., Adamson, D. & Arndtsen, B. A. A novel example of chiral counteranion induced enantioselective metal catalysis: the importance of ion-pairing in copper-catalyzed olefin aziridination and cyclopropanation. Org. Lett. 2, 4165–4168 (2000).
Carter, C., Fletcher, S. & Nelson, A. Towards phase-transfer catalysts with a chiral anion: inducing asymmetry in the reactions of cations. Tetrahedron 14, 1995–2004 (2003).
Alper, H. & Hamel, N. Asymmetric synthesis of acids by the palladium-catalyzed hydrocarboxylation of olefins in the presence of (R)-(–)- or (S)-(+)-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate. J. Am. Chem. Soc. 112, 2803–2804 (1990).
Inanaga, J., Sugimoto, Y. & Hanamoto, T. Achiral and chiral lanthanide(III) salts of superacids as novel Lewis acid catalysts in organic synthesis. New J. Chem. 19, 707–712 (1995).
Hanamoto, T., Furuno, H., Sugimoto, Y. & Inanaga, J. Asymmetric hetero Diels–Alder reaction catalyzed by chiral ytterbium(III) phosphate{Yb[(R)-(–)-BNP]3}: remarkable ligand effect on the enantioselectivity. Synlett 1, 79–80 (1997).
Lacasse, M. C., Poulard, C. & Charette, A. B. Iodomethylzinc phosphates: powerful reagents for the cyclopropanation of alkenes. J. Am. Chem. Soc. 127, 12440–12441 (2005).
Yamamoto, H. & Futatsugi, K. 'Designer acids': combined acid catalysis for asymmetric synthesis. Angew. Chem. Int. Ed. 44, 1924–1942 (2005).
Akiyama, T., Itoh, J., Yokota, K. & Fuchibe, K. Enantioselective Mannich-type reaction catalyzed by a chiral Bronsted acid. Angew. Chem. Int. Ed. 43, 1566–1568 (2004).
Uraguchi, D. & Terada, M. Chiral Bronsted acid-catalyzed direct Mannich reactions via electrophilic activation. J. Am. Chem. Soc. 126, 5356–5357 (2004).
Terada, M. Binaphthol-derived phosphoric acid as a versatile catalyst for enantioselective carbon–carbon bond forming reactions. Chem. Commun. 4097–4112 (2008).
Yang, J. W., Hechavarria Fonseca, M. T., Vignola, N. & List, B. Metal-free, organocatalytic asymmetric transfer hydrogenation of α, β-unsaturated aldehydes. Angew. Chem. Int. Ed. 44, 108–110 (2005).
Ouellet, S. G., Tuttle, J. B. & MacMillan, D. W. Enantioselective organocatalytic hydride reduction. J. Am. Chem. Soc. 127, 32–33 (2005).
Mayer, S. & List, B. Asymmetric counteranion-directed catalysis. Angew. Chem. Int. Ed. 45, 4193–4195 (2006).
Wang, X. & List, B. Asymmetric counteranion-directed catalysis for the epoxidation of enals. Angew. Chem. Int. Ed. 47, 1119–1122 (2008).
Hamilton, G. L., Kanai, T. & Toste, F. D. Chiral anion-mediated asymmetric ring opening of meso-aziridinium and episulfonium ions. J. Am. Chem. Soc. 130, 14984–14986 (2008).
Hennecke, U., Müller, C. H. & Fröhlich, R. Enantioselective haloetherification by asymmetric opening of meso-halonium ions. Org. Lett. 13, 860–863 (2011).
García-García, P., Lay, F., García-García, P., Rabalakos, C. & List, B. A powerful chiral counteranion motif for asymmetric catalysis. Angew. Chem. Int. Ed. 48, 4363–4366 (2009).
Rueping, M., Uria, U., Lin, M-Y. & Atodiresei, I. Chiral organic contact ion pairs in metal-free catalytic asymmetric allylic substitutions. J. Am. Chem. Soc. 133, 3732–3735 (2011).
Aranzamendi, E., Sotomayor, N. & Lete, E. Brønsted acid catalyzed enantioselective α-amidoalkylation in the synthesis of isoindoloisoquinolines. J. Org. Chem. 77, 2986–2991 (2012).
Gómez-SanJuan, A., Sotomayor, N. & Lete, E. Enantioselective intramolecular α-amidoalkylation reaction in the synthesis of pyrrolo[2,1-a]isoquinolines. Tetrahedron Lett. 53, 2157–2159 (2012).
Guo, Q-X. et al. Highly enantioselective alkylation reaction of enamides by Brønsted-acid catalysis. Org. Lett. 11, 4620–4623 (2009).
Terada, M., Tanaka, H. & Sorimachi, K. Enantioselective direct Aldol-type reaction of azlactone via protonation of vinyl ethers by a chiral Brønsted acid catalyst. J. Am. Chem. Soc. 131, 3430–3431 (2009).
Zhang, Q-W. et al. Brønsted acid catalyzed enantioselective semipinacol rearrangement for the synthesis of chiral spiroethers. Angew. Chem. Int. Ed. 48, 8572–8574 (2009).
Čoricć, I., Vellalath, S. & List, B. Catalytic asymmetric transacetalization. J. Am. Chem. Soc. 132, 8536–8537 (2010).
Čoricć, I. & List, B. Asymmetric spiroacetalization catalysed by confined Brønsted acids. Nature 483, 315–319 (2012).
Komanduri, V. & Krische, M. J. Enantioselective reductive coupling of 1,3-enynes to heterocyclic aromatic aldehydes and ketones via rhodium-catalyzed asymmetric hydrogenation: mechanistic insight into the role of Brønsted acid additives. J. Am. Chem. Soc. 128, 16448–16449 (2006).
Shapiro, N. D. & Toste, F. D. A reactivity-driven approach to the discovery and development of gold-catalyzed organic reactions. Synlett 675–691 (2010).
LaLonde, R. L., Sherry, B. D., Kang, E. J. & Toste, F. D. Gold(I)-catalyzed enantioselective intramolecular hydroamination of allenes. J. Am. Chem. Soc. 129, 2452–2453 (2007).
Hamilton, G. L., Kang, E. J., Mba, M. & Toste, F. D. A powerful chiral counterion strategy for asymmetric transition metal catalysis. Science 317, 496–499 (2007).
LaLonde, R. L., Wang, Z. J., Mba, M., Lackner, A. D. & Toste, F. D. Gold(I)-catalyzed enantioselective synthesis of pyrazolidines, isoxazolidines, and tetrahydrooxazines. Angew. Chem. Int. Ed. 49, 598–601 (2010).
Aikawa, K., Kojima, M. & Mikami, K. Synergistic effect: hydroalkoxylation of allenes through combination of enantiopure BIPHEP–gold complexes and chiral anions. Adv. Synth. Cat. 352, 3131–3135 (2010).
Shapiro, N. D., Rauniyar, V., Hamilton, G. L., Wu, J. & Toste, F. D. Asymmetric additions to dienes catalysed by a dithiophosphoric acid. Nature 470, 245–249 (2011).
Mukherjee, S. & List, B. Chiral counteranions in asymmetric transition-metal catalysis: highly enantioselective Pd/Brønsted acid-catalyzed direct alpha-allylation of aldehydes. J. Am. Chem. Soc. 129, 11336–11337 (2007).
Rueping, M., Antonchick, A. P. & Brinkmann, C. Dual catalysis: a combined enantioselective Brønsted acid and metal-catalyzed reaction—metal catalysis with chiral counterions. Angew. Chem. Int. Ed. 46, 6903–6906 (2007).
Campbell, M. J. & Toste, F. D. Enantioselective synthesis of cyclic carbamimidates via a three-component reaction of imines, terminal alkynes, and p-toluenesulfonylisocyanate using a monophosphine gold(I) catalyst. Chem. Sci. 2, 1369–1378 (2011).
Liao, S. & List, B. Asymmetric counteranion-directed transition-metal catalysis: enantioselective epoxidation of alkenes with manganese(III) salen phosphate complexes. Angew. Chem. Int. Ed. 49, 628–631 (2010).
Jiang, G., Halder, R., Fang, Y. & List, B. A highly enantioselective Overman rearrangement through asymmetric counteranion-directed palladium catalysis. Angew. Chem. Int. Ed. 50, 9752–9755 (2011).
Jiang, G. & List, B. Palladium/Brønsted acid-catalyzed α-allylation of aldehydes with allylic alcohols. Adv. Synth. Cat. 353, 1667–1670 (2011).
Jiang, G. & List, B. Direct asymmetric α-allylation of aldehydes with simple allylic alcohols enabled by the concerted action of three different catalysts. Angew. Chem. Int. Ed. 50, 9471–9474 (2011).
Jiang, G. & List, B. Enantioselective hydrovinylation via asymmetric counteranion-directed ruthenium catalysis. Chem. Commun. 47, 10022–10024 (2011).
Li, C., Wang, C., Villa-Marcos, B. & Xiao, J. Chiral counteranion-aided asymmetric hydrogenation of acyclic imines. J. Am. Chem. Soc. 130, 14450–14451 (2008).
Li, C., Villa-Marcos, B. & Xiao, J. Metal−Brønsted acid cooperative catalysis for asymmetric reductive amination. J. Am. Chem. Soc. 131, 6967–6969 (2009).
Rueping, M. & Koenigs, R. M. Bronsted acid differentiated metal catalysis by kinetic discrimination. Chem. Commun. 47, 304–306 (2011).
Chai, Z. & Rainey, T. J. Pd(II)/Brønsted acid catalyzed enantioselective allylic C–H activation for the synthesis of spirocyclic rings. J. Am. Chem. Soc. 134, 3615–3618 (2012).
Zhao, B., Du, H. & Shi, Y. Cu(I)-catalyzed diamination of conjugated olefins with tunable anionic counterions. a possible approach to asymmetric diamination. J. Org. Chem. 74, 8392–8395 (2009).
Yazaki, R., Kumagai, N. & Shibasaki, M. Direct catalytic asymmetric conjugate addition of terminal alkynes to α, β-unsaturated thioamides. J. Am. Chem. Soc. 132, 10275–10277 (2010).
Rauniyar, V., Wang, Z. J., Burks, H. E. & Toste, F. D. Enantioselective synthesis of highly substituted furans by a copper(II)-catalyzed cycloisomerization-indole addition reaction. J. Am. Chem. Soc. 133, 8486–8489 (2011).
Barbazanges, M. et al. Enantioselective IrI-catalyzed carbocyclization of 1,6-enynes by the chiral counterion strategy. Chem. Eur. J. 17, 13789–13794 (2011).
Zbieg, J. R., Yamaguchi, E., McInturff, E. L. & Krische, M. J. Enantioselective C–H crotylation of primary alcohols via hydrohydroxyalkylation of butadiene. Science 336, 324–327 (2012).
Ohmatsu, K., Ito, M., Kunieda, T. & Ooi, T. Ion-paired chiral ligands for asymmetric palladium catalysis. Nature Chem. 4, 473–477 (2012).
Belokon, Y. N. et al. Potassium and silver chiral cobaltate(III) complexes as precatalysts for asymmetric C–C bond formation. Tetrahedron 19, 822–831 (2008).
Zhang, Z. & Schreiner, P. R. (Thio)urea organocatalysis: What can be learnt from anion recognition? Chem. Soc. Rev. 38, 1187–1198 (2009).
Kotke, M. & Schreiner, P. R. Acid-free, organocatalytic acetalization. Tetrahedron 62, 434–439 (2006).
Kotke, M. & Schreiner, P. R. Generally applicable organocatalytic tetrahydropyranylation of hydroxy functionalities with very low catalyst loading. Synthesis 5, 779–790 (2007).
Taylor, M. S. & Jacobsen, E. N. Highly enantioselective catalytic acyl-Pictet–Spengler reactions. J. Am. Chem. Soc. 126, 10558–10559 (2004).
Taylor, M. S., Tokunaga, N. & Jacobsen, E. N. Enantioselective thiourea-catalyzed acyl-Mannich reactions of isoquinolines. Angew. Chem. Int. Ed. 44, 6700–6704 (2005).
Raheem, I. T., Thiara, P. S., Peterson, E. A. & Jacobsen, E. N. Enantioselective Pictet–Spengler-type cyclizations of hydroxylactams: H-bond donor catalysis by anion binding. J. Am. Chem. Soc. 129, 13404–13405 (2007).
Raheem, I. T., Thiara, P. S. & Jacobsen, E. N. Regio- and enantioselective catalytic cyclization of pyrroles onto N-acyliminium ions. Org. Lett. 10, 1577–1580 (2008).
Reisman, S. E., Doyle, A. G. & Jacobsen, E. N. Enantioselective thiourea-catalyzed additions to oxocarbenium ions. J. Am. Chem. Soc. 130, 7198–7199 (2008).
Knowles, R. R., Lin, S. & Jacobsen, E. N. Enantioselective thiourea-catalyzed cationic polycyclizations. J. Am. Chem. Soc. 132, 5030–5032 (2010).
Brown, A. R., Kuo, W-H. & Jacobsen, E. N. Enantioselective catalytic alpha-alkylation of aldehydes via an SN1 pathway. J. Am. Chem. Soc. 132, 9286–9288 (2010).
Birrell, J. A., Desrosiers, J-N. & Jacobsen, E. N. Enantioselective acylation of silyl ketene acetals through fluoride anion-binding catalysis. J. Am. Chem. Soc. 133, 13872–13875 (2011).
Wurz, R. P. Chiral dialkylaminopyridine catalysts in asymmetric synthesis. Chem. Rev. 107, 5570–5595 (2007).
De, C. K., Klauber, E. G. & Seidel, D. Merging nucleophilic and hydrogen bonding catalysis: an anion binding approach to the kinetic resolution of amines. J. Am. Chem. Soc. 131, 17060–17061 (2009).
Klauber, E. G., De, C. K., Shah, T. K. & Seidel, D. Merging nucleophilic and hydrogen bonding catalysis: an anion binding approach to the kinetic resolution of propargylic amines. J. Am. Chem. Soc. 132, 13624–13626 (2010).
De, C. K. & Seidel, D. Catalytic enantioselective desymmetrization of meso-diamines: a dual small-molecule catalysis approach. J. Am. Chem. Soc. 133, 14538–14541 (2011).
De, C. K., Mittal, N. & Seidel, D. A Dual-catalysis approach to the asymmetric Steglich rearrangement and catalytic enantioselective addition of O-acylated azlactones to isoquinolines. J. Am. Chem. Soc. 133, 16802–16805 (2011).
Rauniyar, V., Lackner, A. D., Hamilton, G. L. & Toste, F. D. Asymmetric electrophilic fluorination using an anionic chiral phase-transfer catalyst. Science 334, 1681–1684 (2011).
Phipps, R. J., Hiramatsu, K. & Toste, F. D. Asymmetric fluorination of enamides: access to α-fluoroimines using an anionic chiral phase-transfer catalyst. J. Am. Chem. Soc. 134, 8376–8379 (2012).
Acknowledgements
We thank the University of California, Berkeley, US Department of Energy under contract no. DE-AC02-05CH11231 and NIHGMS (RO1 GM073932) for financial support. R.J.P. is grateful to the European Commission for a Marie Curie International Outgoing Fellowship.
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Phipps, R., Hamilton, G. & Toste, F. The progression of chiral anions from concepts to applications in asymmetric catalysis. Nature Chem 4, 603–614 (2012). https://doi.org/10.1038/nchem.1405
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DOI: https://doi.org/10.1038/nchem.1405
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