Abstract
Highly enantioselective production of chiral compounds by chiral catalysis is one of the most challenging forms of catalytic selectivity. In this perspective, we argue by examples that the key to achieving high enantioselectivity lies in processes with non-linear kinetics or equilibria that effectively amplify small differences in enantiospecific energetics. Examples of such processes have been uncovered over the past decade and include autocatalysis, surface explosion reactions, stirring or grinding of crystallites, and cooperative self-assembly.
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Bolm C, Gladysz JA (2003) Introduction: enantioselective catalysis. Chem Rev 103(8):2761–2762
Siegel JS (1998) Homochiral imperative of molecular evolution. Chirality 10(1–2):24–27
Nguyen LA, He H, Pham-Huy C (2006) Chiral drugs: an overview. Int J Biomed Sci 2(2):85–100
Zaera F (2017) Chirality in adsorption on solid surfaces. Chem Soc Rev 46(23):7374–7398
Gellman AJ, Tysoe WT, Zaera F (2015) Surface chemistry for enantioselective catalysis. Catal Lett 145(1):220–232
Ernst KH (2012) Molecular chirality at surfaces. Phys Status Solidi B 249(11):2057–2088
Jenkins SJ, Pratt SJ (2007) Beyond the surface atlas: a roadmap and gazetteer for surface symmetry and structure. Surf Sci Rep 62(10):373–429
McFadden CF, Cremer PS, Gellman AJ (1996) Adsorption of chiral alcohols on ‘‘chiral’’ metal surfaces. Langmuir 12(10):2483–2487
Yun Y, Gellman AJ (2015) Enantiospecific adsorption of amino acids on naturally chiral Cu{3,1,17}(R&S) surfaces. Langmuir 31(22):6055–6063
Yun YJ, Wei D, Sholl DS, Gellman AJ (2014) Equilibrium adsorption of D- and L-Alanine mixtures on naturally chiral Cu{3,1,17}(R&S) surfaces. J Phys Chem C 118(27):14957–14966
Yun YJ, Gellman AJ (2013) Enantioselective separation on naturally chiral metal surfaces: D,L-aspartic acid on Cu(3,1,17) (R&S) surfaces. Angew Chem Int Ed 52(12):3394–3397
Gellman AJ, Huang Y, Koritnik AJ, Horvath JD (2017) Structure-sensitive enantiospecific adsorption on naturally chiral Cu(hkl) (R&S) surfaces. J Phys Condens Matter 29(3):034001
Horvath JD, Gellman AJ (2002) Enantiospecific desorption of chiral compounds from chiral Cu(643) and achiral Cu(111) surfaces. J Am Chem Soc 124(10):2384–2392
Horvath JD, Gellman AJ (2001) Enantiospecific desorption of R- and S-propylene oxide from a chiral Cu(643) surface. J Am Chem Soc 123(32):7953–7954
Blackmond DG (2010) Kinetic aspects of non-linear effects in asymmetric synthesis, catalysis, and autocatalysis. Tetrahedron Asymmetry 21(11–12):1630–1634
Saito Y, Hyuga H, Colloquium (2013) Homochirality: symmetry breaking in systems driven far from equilibrium. Rev Mod Phys 85(2):603–621
Ahuja S (2000) Chiral separations by chromatography. Oxford University Press, Washington, DC
Pilling MJ, Seakins PW (1995) Reaction kinetics, 1st edn., Oxford University Press, Washington, DC
Vanhove D (1996) Catalyst testing at a lab scale in mild oxidation: can you control the reaction temperature? Appl Catal A 138(2):215–234
Williams KA, Schmidt LD (2006) Catalytic autoignition of higher alkane partial oxidation on Rh-coated foams. Appl Catal A 299:30–45
Kimmerle B, Grunwaldt JD, Baiker A, Glatzel P, Boye P, Stephan S, Schroer CG (2009) Visualizing a catalyst at work during the ignition of the catalytic partial oxidation of methane. J Phys Chem C 113(8):3037–3040
Steinfeld JI, Francisco JS, Hase WL (1989) Chemical kinetics and dynamics. Prentice-Hall, Inc., Upper Saddle River
Frank FC (1953) On spontaneous asymmetric synthesis. Biochem Biophys Acta 11(4):459–463
Bonner WA (1991) The Origin and amplification of biomolecular chirality. Orig Life Evol Biosph 21(2):59–111
Soai K, Niwa S, Hori H (1990) Asymmetric self-catalytic reaction—self-production of chiral 1-(3-Pyridyl)alkanols as chiral self-catalysts in the enantioselective addition of dialkylzinc reagents to pyridine-3-carbaldehyde. J Chem Soc Chem Commun 14:982–983
Gehring T, Busch M, Schlageter M, Weingand D (2010) A concise summary of experimental facts about the soai reaction. Chirality 22(1E):E173–E182
Mauksch M, Tsogoeva SB, Wei SW, Martynova IM (2007) Demonstration of spontaneous chiral symmetry breaking in asymmetric mannich and aldol reactions. Chirality 19(10):816–825
Mauksch M, Tsogoeva SB, Martynova IM, Wei SW (2007) Evidence of asymmetric autocatalysis in organocatalytic reactions. Angew Chem Int Ed 46(3):393–396
Shibata T, Morioka H, Hayase T, Choji K, Soai K (1996) Highly enantioselective catalytic asymmetric automultiplication of chiral pyrimidyl alcohol. J Am Chem Soc 118(2):471–472
Shibata T, Yonekubo S, Soai K (1999) Practically perfect asymmetric autocatalysis with (2-alkynyl-5-pyrimidyl)alkanols. Angew Chem Int Ed 38(5):659–661
Sato I, Yanagi T, Soai K (2002) Highly enantioselective asymmetric autocatalysis of 2-alkenyl- and 2-vinyl-5-pyrimidyl alkanols with significant amplification of enantiomeric excess. Chirality 14(2–3):166–168
Soai K, Osanai S, Kadowaki K, Yonekubo S, Shibata T, Sato I (1999) D- and L-quartz-promoted highly enantioselective synthesis of a chiral organic compound. J Am Chem Soc 121(48):11235–11236
Kawasaki T, Okano Y, Suzuki E, Takano S, Oji S, Soai K (2011) Asymmetric autocatalysis: triggered by chiral isotopomer arising from oxygen isotope substitution. Angew Chem Int Ed 50(35):8131–8133
McCarty J, Falconer J, Madix RJ (1973) Decomposition of formic acid on Ni(110). 1. Flash decomposition from clean surface and flash desorption of reaction products. J Catal 30(2):235–249
Redhead PA (1962) Thermal desorption of gases. Vacuum 12:203–211
Falconer JL, McCarty JG, Madix RJ (1974) Surface explosion—HCOOH on Ni(110). Surf Sci 42(1):329–330
Sharpe RG, Bowker M (1995) Kinetic-models of surface explosions. J Phys Condens Matter 7(32):6379–6392
Bowker M, Cassidy TJ, Allen MD, Li Y (1994) Surface explosions of acetate intermediates on Rh crystals and catalysts. Surf Sci 309:143–146
Cassidy TJ, Allen MD, Li Y, Bowker M (1993) From surface science to catalysis—surface explosions observed on Rh crystals and supported catalysts. Catal Lett 21(3–4):321–331
Behzadi B, Romer S, Fasel R, Ernst KH (2004) Chiral recognition in surface explosion. J Am Chem Soc 126(30):9176–9177
Lorenzo MO, Humblot V, Murray P, Baddeley CJ, Haq S, Raval R, Transformations C (2002) Molecular transport, and kinetic barriers in creating the chiral phase of (R,R)-tartaric acid on Cu(110). J Catal 205(1):123–134
Romer S, Behzadi B, Fasel R, Ernst KH (2005) Homochiral conglomerates and racemic crystals in two dimensions: tartaric acid on Cu(110). Chem Eur J 11(14):4149–4154
Merz L, Ernst KH (2010) Unification of the matrix notation in molecular surface science. Surf Sci 604(11–12):1049–1054
Gellman AJ, Huang Y, Feng X, Pushkarev VV, Holsclaw B, Mhatre BS (2013) Superenantioselective chiral surface explosions. J Am Chem Soc 135(51):19208–19214
Mhatre BS, Dutta S, Reinicker A, Karagoz B, Gellman AJ (2016) Explosive enantiospecific decomposition of aspartic acid on Cu surfaces. Chem Commun 52(98):14125–14128
Hazen RM, Filley TR, Goodfriend GA (2001) Selective adsorption of L- and D-amino acids on calcite: implications for biochemical homochirality. Proc Natl Acad Sci USA 98(10):5487–5490
Cundy KC, Crooks PA (1983) Unexpected phenomenon in the high performance liquid-chromatographic analysis of racemic 14C-labeled nicotine—separation of enantiomers in a totally achiral system. J Chromatogr 281:17–33
Soloshonok VA (2006) Remarkable amplification of the self-disproportionation of enantiomers on achiral-phase chromatography columns. Angew Chem Int Ed 45(5):766–769
Soloshonok VA, Roussel C, Kitagawa O, Sorochinsky AE (2012) Self-disproportionation of enantiomers via achiral chromatography: a warning and an extra dimension in optical purifications. Chem Soc Rev 41(11):4180–4188
Yun Y, Gellman AJ (2016) Competing forces in chiral surface chemistry: enantiospecificity versus enantiomer aggregation. J Phys Chem C 120(48):27285–27295
Yun YJ, Gellman AJ (2015) Adsorption-induced auto-amplification of enantiomeric excess on an achiral surface. Nat Chem 7(6):520–525
Green MM, Park JW, Sato T, Teramoto A, Lifson S, Selinger RLB, Selinger JV (1999) The macromolecular route to chiral amplification. Angew Chem Int Ed 38(21):3139–3154
Green MM, Reidy MP, Johnson RJ, Darling G, Oleary DJ, Willson G (1989) Macromolecular stereochemistry—the out-of-proportion influence of optically-active Co-monomers on the conformational characteristics of polyisocyanates—the sergeants and soldiers experiment. J Am Chem Soc 111(16):6452–6454
Green MM, Garetz BA, Munoz B, Chang HP, Hoke S, Cooks RG (1995) Majority rules in the copolymerization of mirror-image isomers. J Am Chem Soc 117(14):4181–4182
Palmans ARA, Meijer EW (2007) Amplification of chirality in dynamic supramolecular aggregates. Angew Chem Int Ed 46(47):8948–8968
van Gestel J, Palmans ARA, Titulaer B, Vekemans J, Meijer EW (2005) “Majority-rules” operative in chiral columnar stacks of C-3-symmetrical molecules. J Am Chem Soc 127(15):5490–5494
Ernst KH (2010) Amplification of chirality at solid surfaces. Orig Life Evol Biosph 40(1):41–50
Humblot V, Lorenzo MO, Baddeley CJ, Haq S, Raval R (2004) Local and global chirality at surfaces: succinic acid versus tartaric acid on Cu(110). J Am Chem Soc 126(20):6460–6469
Parschau M, Romer S, Ernst KH (2004) Induction of homochirality in achiral enantiomorphous monolayers. J Am Chem Soc 126(47):15398–15399
Parschau M, Kampen T, Ernst KH (2005) Homochirality in Monolayers of achiral meso tartaric acid. Chem Phys Lett 407(4–6):433–437
Barbosa L, Sautet P (2001) Stability of chiral domains produced by adsorption of tartaric acid isomers on the Cu(110) surface: a periodic density functional theory study. J Am Chem Soc 123(27):6639–6648
Fasel R, Wider J, Quitmann C, Ernst KH, Greber T (2004) Determination of the absolute chirality of adsorbed molecules. Angew Chem Int Ed 43(21):2853–2856
Roth C, Passerone D, Merz L, Parschau M, Ernst KH (2011) Two-dimensional self-assembly of chiral malic acid on Cu(110). J Phys Chem C 115(4):1240–1247
Karageorgaki C, Ernst KH (2014) A metal surface with chiral memory. Chem Commun 50(15):1814–1816
Karageorgaki C, Passerone D, Ernst KH (2014) Chiral reconstruction of Cu(110) after adsorption of fumaric acid. Surf Sci 629:75–80
Fang Y, Ghijsens E, Ivasenko O, Cao H, Noguchi A, Mali KS, Tahara K, Tobe Y, De Feyter S (2016) Dynamic control over supramolecular handedness by selecting chiral induction pathways at the solution-solid interface. Nat Chem 8(7):711–717
Chen T, Yang WH, Wang D, Wan LJ (2013) Globally homochiral assembly of two-dimensional molecular networks triggered by co-absorbers. Nat Commun 4:1389
Katsonis N, Xu H, Haak RM, Kudernac T, Tomovic Z, George S, Van der Auweraer M, Schenning A, Meijer EW, Feringa BL, De Feyter S (2008) Emerging solvent-induced homochirality by the confinement of achiral molecules against a solid surface. Angew Chem Int Ed 47(27):4997–5001
Fasel R, Parschau M, Ernst KH (2006) Amplification of chirality in two-dimensional enantiomorphous lattices. Nature 439(7075):449–452
Parschau M, Fasel R, Ernst KH (2008) Coverage and enantiomeric excess dependent enantiomorphism in two-dimensional molecular crystals. Cryst Growth Des 8(6):1890–1896
Fasel R, Parschau M, Ernst KH (2003) Chirality transfer from single molecules into self-assembled monolayers. Angew Chem Int Ed 42(42):5178–5181
Chen Q, Lee CW, Frankel DJ, Richardson NV (1999) The formation of enantiospecific phases on a Cu{110} surface. PhysChemComm 2(9):41–44
Haq S, Liu N, Humblot V, Jansen APJ, Raval R (2009) Drastic symmetry breaking in supramolecular organization of enantiomerically unbalanced monolayers at surfaces. Nat Chem 1(5):409–414
Roth C, Passerone D, Ernst KH (2010) Pasteur’s quasiracemates in 2D: chiral conflict between structurally different enantiomers induces single-handed enantiomorphism. Chem Commun 46(45):8645–8647
Seibel J, Allemann O, Siegel JS, Ernst KH (2013) Chiral conflict among different helicenes suppresses formation of one enantiomorph in 2D crystallization. J Am Chem Soc 135(20):7434–7437
Kipping F, Pope W (1898) LXIII.—Enantiomorphism J Chem Soc 73:606–617
Kondepudi DK, Kaufman RJ, Singh N (1990) Chiral symmetry breaking in sodium-chlorate crystallization. Science 250(4983):975–976
McBride JM, Carter RL (1991) Spontaneous resolution by stirred crystallization. Angew Chem Int Ed Engl 30(3):293–295
Gernez MD (1867) Séparation des tartrates gauches et des tartrates droits, À L’aide Des solutions sursaturées. J Pharm Chim 4(5):111–115
Viedma C (2005) Chiral symmetry breaking during crystallization: complete chiral purity induced by nonlinear autocatalysis and recycling. Phys Rev Lett 94(6):065504
Noorduin WL, Meekes H, van Enckevort WJP, Millemaggi A, Leeman M, Kaptein B, Kellogg RM, Vlieg E (2008) Complete deracemization by attrition-enhanced ostwald ripening elucidated. Angew Chem Int Ed 47(34):6445–6447
Saito Y, Hyuga H (2008) Chiral crystal growth under grinding. J Phys Soc Jpn 77(11):113001
Liesegang RE (1911) Zur übersättigungstheorie einiger scheinbar rhythmischer reaktionen. Z Phys Chem 75:371–373
McBride JM, Tully JC (2008) Physical chemistry—did life grind to a start? Nature 452(7184):161–162
Noorduin WL, van Enckevort WJP, Meekes H, Kaptein B, Kellogg RM, Tully JC, McBride JM, Vlieg E (2010) The driving mechanism behind attrition-enhanced deracemization. Angew Chem Int Ed 49(45):8435–8438
Viedma C, McBride JM, Kahr B, Cintas P (2013) Enantiomer-specific oriented attachment: formation of macroscopic homochiral crystal aggregates from a racemic system. Angew Chem Int Ed 52(40):10545–10548
De Yoreo JJ, Gilbert P, Sommerdijk N, Penn RL, Whitelam S, Joester D, Zhang HZ, Rimer JD, Navrotsky A, Banfield JF, Wallace AF, Michel FM, Meldrum FC, Colfen H, Dove PM (2015) Crystallization by particle attachment in synthetic, biogenic, and geologic environments. Science 349(6247):aaa6760
Viedma C, Cuccia LA, McTaggart A, Kahr B, Martin AT, McBride JM, Cintas P (2016) Oriented attachment by enantioselective facet recognition in millimeter-sized gypsum crystals. Chem Commun 52(78):11673–11676
El-Hachemi Z, Crusats JQ, Ribo JM, Veintemillas-Verdaguer S (2009) Spontaneous transition toward chirality in the NaClO3 crystallization in boiling solutions. Cryst Growth Des 9(11):4802–4806
El-Hachemi Z, Crusats J, Ribo JM, McBride JM, Veintemillas-Verdaguer S (2011) Metastability in supersaturated solution and transition towards chirality in the crystallization of NaClO3. Angew Chem Int Ed 50(10):2359–2363
Weissbuch I, Leiserowitz L, Lahav M (2005) Stochastic “mirror symmetry breaking” via self-assembly, reactivity and amplification of chirality: relevance to abiotic conditions. In: Walde P (ed) Prebiotic chemistry: from simple amphiphiles to protocell models. vol 259, Springer, Berlin, pp 123–165
Frank P, Bonner W, Zare R (2001) On one hand but not the other: the challenge of the origin and survival of homochirality in prebiotic chemistry. Wiley, Weinheim
Acknowledgements
AJG acknowledges support from the US Dept. of Energy under Grant No. DE-SC0008703. Support by the Schweizerischer Nationalfonds zur Förderung der Wissenschaften (grants # 200020_163296, 200021_152559, CRSII5_173720) is gratefully acknowledged. KHE thanks Jack Dunitz, Bart Kahr and Meir Lahav for fruitful discussions.
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Gellman, A.J., Ernst, KH. Chiral Autocatalysis and Mirror Symmetry Breaking. Catal Lett 148, 1610–1621 (2018). https://doi.org/10.1007/s10562-018-2380-x
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DOI: https://doi.org/10.1007/s10562-018-2380-x