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2015 | 2 | 1 |

Article title

Catalytic Supramolecular Photochirogenesis


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Supramolecular photochirogenesis is a new
strategy for circumventing the inherent difficulties
encountered in conventional photochirogenesis, i.e. the
interactions associated with geometrically less-defined,
short-lived excited states, by confining a prochiral
substrate(s) in a chiral supramolecular environment(s)
prior to photoexcitation. This rather simple, but very
successful, strategy has been applied to a variety of
chiral photoreactions. However, a stoichiometric, or
even excess amount of supramolecular host is often
needed to ensure full complexation of the substrate,
and achieve the optimum stereochemical outcome.
This apparent drawback has recently been removed by
introducing a sensitizing moiety to the supramolecular
host, or by bathochromically shifting the absorption
band of substrate through Lewis acid, or charge-transfer
complexation. Recent progress in catalytic supramolecular
photochirogenesis will be reviewed.







Physical description


23 - 3 - 2015
3 - 2 - 2015
3 - 7 - 2015


  • Key Laboratory of Green
    Chemistry & Technology of Ministry of Education, College of Chemistry
    and State Key Laboratory of Biotherapy, West China Medical
    School, Sichuan University, 29 Wangjiang Road, Chengdu 610064,
  • Key Laboratory of Green
    Chemistry & Technology of Ministry of Education, College of Chemistry
    and State Key Laboratory of Biotherapy, West China Medical
    School, Sichuan University, 29 Wangjiang Road, Chengdu 610064,
  • Key Laboratory of Green
    Chemistry & Technology of Ministry of Education, College of Chemistry
    and State Key Laboratory of Biotherapy, West China Medical
    School, Sichuan University, 29 Wangjiang Road, Chengdu 610064,
  • Department of Applied
    Chemistry, Osaka University, 2-1 Yamada-oka, Suita 565-0871,


  • ---
  • [1] Yang C., Inoue Y., CRC Handbook of Organic Photochemistryand Photobiology (3rd ed), 2012, pp. 125-176.
  • [2] Inoue Y., Ramamurthy V., Chiral Photochemistry, Marcel Dekker,2004.
  • [3] Axel G. Griesbeck, Meierhenrich U.J., Asymmetricphotochemistry and photochirogenesis, Angew. Chem. Int. Ed.,2002, 41, 3147-3154.
  • [4] Mueller C., Bach T., Chirality Control in PhotochemicalReactions: Enantioselective Formation of ComplexPhotoproducts in Solution, Aust. J. Chem., 2008, 61, 557-564. T.Bach in Asymmetric Synthesis-The Essentials (Eds.: S. Bräse,M. Christmann), Wiley-VCH, Weinheim, 2006, pp. 166-170
  • [5] Hammond G.S., Cole R.S., Asymmetric induction during energytransfer, J. Am. Chem. Soc., 1965, 87, 3256-3257.
  • [6] Inoue Y., Yokoyama T., Yamasaki N., Tai A., An optical yieldthat increases with temperature in a photochemically inducedenantiomeric isomerization, Nature, 1989, 341, 225-226.
  • [7] Inoue Y., Yokoyama T., Yamasaki N., Tai A., Temperatureswitching of product chirality upon photosensitized enantiodifferentiatingcis-trans isomerization of cyclooctene, J. Am.Chem. Soc., 1989, 111, 6480-6482.
  • [8] Inoue Y., Matsushima E., Wada T., Pressure and temperaturecontrol of product chirality in asymmetric photochemistry.enantiodifferentiating photoisomerization of cyclooctenesensitized by chiral benzenepolycarboxylates, J. Am. Chem.Soc., 1998, 120, 10687-10696.
  • [9] Maeda R., Wada T., Mori T., Kono S., Kanomata N., Inoue Y.,Planar-to-planar chirality transfer in the excited state. enantiodifferentiatingphotoisomerization of cyclooctenes sensitizedby planar-chiral paracyclophane, J. Am. Chem. Soc., 2011, 133,10379-10381.
  • [10] Vallavoju N., Sivaguru J., Supramolecular photocatalysis:Combining confinement and non-covalent interactions tocontrol light initiated reactions. Chem. Soc. Rev., 2014, 43,4084-4101.
  • [11] Yang C., Inoue Y., Supramolecular photochirogenesis, Chem.Soc. Rev., 2014, 43, 4123-4143.
  • [12] Nakamura A., Inoue Y., Supramolecular catalysis of theenantiodifferentiating
  • [4+4] photocyclodimerization of2-anthracenecarboxylate by g-cyclodextrin, J. Am. Chem. Soc.,2003, 125, 966-972.
  • [13] Luo L., Liao G.H., Wu X.L., Lei L., Tung C.H., Wu L.Z.,g-Cyclodextrin-directed enantioselective photocyclodimerizationof methyl 3-methoxyl-2-naphthoate, J. Org. Chem.,2009, 74, 3506-3515.
  • [14] Bach T., Grosch B., Strassner T., Herdtweck E., Enantioselective
  • [6p]-photocyclization reaction of an acrylanilide mediated bya chiral host. interplay between enantioselective ring closureand enantioselective protonation, J. Org. Chem., 2003, 68,1107-1116.
  • [15] Sivaguru J., Natarajan A., Kaanumalle L.S., Shailaja J., UppiliS., Joy A., Ramamurthy V., Asymmetric photoreactions withinzeolites: role of confinement and alkali metal ions, Acc. Chem.Res., 2003, 36, 509-521.
  • [16] Nishioka Y., Yamaguchi T., Kawano M., Fujita M., Asymmetric
  • [2+2] olefin cross photoaddition in a self-assembled hostwith remote chiral auxiliaries, J. Am. Chem. Soc., 2008, 130,8160-8161.
  • [17] Ishida Y., Kai Y., Kato S.-y., Misawa A., Amano S., MatsuokaY., Saigo K., Two-component liquid crystals as chiral reactionmedia: highly enantioselective photodimerization of ananthracene derivative driven by the ordered microenvironment,Angew. Chem. Int. Ed., 2008, 47, 8241-8245.
  • [18] Dawn A., Shiraki T., Haraguchi S., Sato H., Sada K., ShinkaiS., Transcription of chirality in the organogel systems dictatesthe enantiodifferentiating photodimerization of substitutedanthracene, Chem. Eur. J., 2010, 16, 3676-3689.
  • [19] Rekharsky M.V., Inoue Y., Complexation thermodynamics ofcyclodextrins, Chem. Rev., 1998, 98, 1875-1918.
  • [20] Yang C., Recent progress in supramolecular chiralphotochemistry, Chin. Chem. Lett., 2013, 24, 437-441.
  • [21] Inoue Y., Dong S.F., Yamamoto K., Tong L.-H., Tsuneishi H.,Hakushi T., Tai A., Inclusion-enhanced optical yield andE/Z ratio in enantiodifferentiating photoisomerization ofcyclooctene included and sensitized by b-cyclodextrinmonobenzoate, J. Am. Chem. Soc., 1995, 117, 11033-11034.
  • [22] Inoue Y., Kosaka S., Matsumoto K., Tsuneishi H., Hakushi T.,Tai A., Nakagawa K., Tong L.-H., Vacuum UV photochemistry incyclodextrin cavities. Solid state Z-E photoisomerization of acyclooctene-b-cyclodextrin inclusion complex, J. Photochem.Photobiol., A, 1993, 71, 61-64.
  • [23] Inoue Y., Wada T., Sugahara N., Yamamoto K., Kimura K., TongL.-H., Gao X.-M., Hou Z.-J., Liu| Y., Supramolecular photochirogenesis.2. enantiodifferentiating photoisomerizationof cyclooctene included and sensitized by 6-O-modifiedcyclodextrins, J. Org. Chem., 2000, 65, 8041-8050.
  • [24] Gao Y., Inoue M., Wada T., Inoue Y., Supramolecular photochirogenesis.3. enantiodifferentiating photoisomerization ofcyclooctene included and sensitized by 6-O-mono(o-methoxybenzoyl)cyclodextrin, J. Incl. Phenom. Macrocycl. Chem., 2004,50, 111-118.
  • [25] Gao Y., Wada T., Yang K., Kim K., Inoue Y., Supramolecularphotochirogenesis in sensitizing chiral nanopore: Enantiodifferentiatingphotoisomerization of (Z)-cyclooctene included andsensitized by POST-1, Chirality, 2005, 17, S19-S23.
  • [26] Lu R., Yang C., Cao Y., Tong L., Jiao W., Wada T., Wang Z., MoriT., Inoue Y., Enantiodifferentiating photoisomerization ofcyclooctene included and sensitized by aroyl-β-cyclodextrins:a critical enantioselectivity control by substituents, J. Org.Chem., 2008, 73, 7695-7701.
  • [27] Lu R., Yang C., Cao Y., Wang Z., Wada T., Jiao W., Mori T., InoueY., Supramolecular enantiodifferentiating photoisomerizationof cyclooctene with modified b-cyclodextrins: critical control bya host structure, Chem. Commun., 2008, 374-376.
  • [28] Liang W., Yang C., Nishijima M., Fukuhara G., Mori T., MeleA., Castiglione F., Caldera F., Trotta F., Inoue Y., Cyclodextrinnanosponge-sensitized enantiodifferentiating photoisomerizationof cyclooctene and 1,3-cyclooctadiene, Beilstein J. Org.Chem., 2012, 8, 1305-1311.
  • [29] Fukuhara G., Mori T., Wada T., Inoue Y., Entropy-controlledsupramolecular photochirogenesis: enantiodifferentiating Z-Ephotoisomerization of cyclooctene included and sensitized bypermethylated 6-O-benzoyl-b-cyclodextrin, Chem. Commun.,2005, 4199-4200.
  • [30] Yang C., Mori T., Wada T., Inoue Y., Supramolecular enantiodifferentiatingphotoisomerization of (Z,Z)-1,3-cyclooctadieneincluded and sensitized by naphthalene-modifiedcyclodextrins, New J. Chem., 2007, 31, 697-702.
  • [31] Fukuhara G., Mori T., Wada T., Inoue Y., Entropy-controlledsupramolecular photochirogenesis: enantiodifferentiating Z-Ephotoisomerization of cyclooctene included and sensitized bypermethylated 6-O-modified b-cyclodextrins, J. Org. Chem.,2006, 71, 8233-8243.
  • [32] Inoue Y., Ikeda H., Kaneda M., Sumimura T., Everitt S.R.L., WadaT., Entropy-controlled asymmetric photochemistry: switchingof product chirality by solvent, J. Am. Chem. Soc., 2000, 122,406-407.
  • [33] Fukuhara G., Klaerner F.-G., Mori T., Wada T., Inoue Y., Supramolecularcomplexation and photochirogenesis with inherentlychiral molecular clip: enantiodifferentiating photoisomerizationof (Z,Z)-1,3-cyclooctadiene and polar photoadditionto 1,1-diphenylpropene, Photochem. Photobiol. Sci., 2008, 7,1493-1500.
  • [34] Inoue Y., Tsuneishi H., Hakushi T., Tai A., Optically active(E,Z)-1,3-cyclooctadiene: First enantioselective synthesisthrough asymmetric photosensitization and chiropticalproperty, J. Am. Chem. Soc., 1997, 119, 472-478.
  • [35] Liang W., Yang C., Zhou D., Haneoka H., Nishijima M., FukuharaG., Mori T., Castiglione F., Mele A., Caldera F., Trotta F., InoueY., Phase-controlled supramolecular photochirogenesisin cyclodextrin nanosponges, Chem. Commu., 2013, 49,3510-3512.
  • [36] Wei X., Liang W., Wu W., Yang C., Trotta F., Caldera F., MeleA., Nishimoto T., Inoue Y., Solvent- and phase-controlledphotochirogenesis. enantiodifferentiating photoisomerizationof (Z)-cyclooctene sensitized by cyclic nigerosylnigerose-basednanosponges crosslinked by pyromellitate, Org. Biomol. Chem.2015, DOI: 10.1039/C4OB02390K in press.
  • [37] Koodanjeri S., Ramamurthy V., Cyclodextrin mediated enantioand diastereoselective geometric photoisomerization ofdiphenylcyclopropane and its derivatives, Tetrahedron Lett.,2002, 43, 9229-9232.
  • [38] Yang C., Fukuhara G., Nakamura A., Origane Y., Fujita K.,Yuan D.-Q., Mori T., Wada T., Inoue Y., Enantiodifferentiating
  • [4+4] photocyclodimerization of 2-anthracenecarboxylatecatalyzed by 6a,6x-diamino-6A,6X-dideoxy-g-cyclodextrins:Manipulation of product chirality by electrostatic interaction,temperature and solvent in supramolecular photochirogenesis,J. Photochem. Photobiol. A: Chem., 2005, 173, 375-384.
  • [39] Yang C., Nakamura A., Fukuhara G., Origane Y., Mori T.,Wada T., Inoue Y., Pressure and temperature-controlledenantiodifferentiating
  • [4+4]-photocyclodimerization of2-anthracenecarboxylate mediated by secondary face- andskeleton-modified gamma -cyclodextrins, J. Org. Chem., 2006,71, 3126-3135.
  • [40] Yang C., Nakamura A., Wada T., Inoue Y., Enantiodifferentiatingphotocyclodimerization of 2-anthracenecarboxylic acidmediated by gamma -cyclodextrins with a flexible or rigid cap,Org. Lett., 2006, 8, 3005-3008.
  • [41] Yang C., Ke C., Fujita K., Yuan D.-Q., Mori T., Inoue Y.,pH-Controlled supramolecular enantiodifferentiating photocyclodimerizationof 2-anthracenecarboxylate with cappedg-cyclodextrins, Aust. J. Chem., 2008, 1-4.
  • [42] Yang C., Mori T., Inoue Y., Supramolecular enantiodifferentiatingphotocyclodimerization of 2-anthracenecarboxylatemediated by capped g-cyclodextrins: critical control of enantioselectivityby cap rigidity, J. Org. Chem., 2008, 73, 5786-5794.
  • [43] Yang C., Mori T., Origane Y., Ko Y.H., Selvapalam N., KimK., Inoue Y., Highly stereoselective photocyclodimerizationof a-cyclodextrin-appended anthracene mediated byg-cyclodextrin and cucurbit
  • [8]uril: a dramatic steric effectoperating outside the binding site, J. Am. Chem. Soc., 2008,130, 8574-8575.
  • [44] Yang C., Ke C., Liang W., Fukuhara G., Mori T., Liu Y., InoueY., Dual Supramolecular photochirogenesis: ultimate stereocontrolof photocyclodimerization by a chiral scaffold andconfining host, J. Am. Chem. Soc., 2011, 133, 13786-13789.
  • [45] Yao J., Yan Z., Ji J., Wu W., Yang C., Nishijima M., FukuharaG., Mori T., Inoue Y., Ammonia-driven chirality inversion andenhancement in enantiodifferentiating photocyclodimerizationof 2-anthracencarboxylate mediated by diguanidino-gcyclodextrin,J. Am. Chem. Soc., 2014, 136, 6916-6919.
  • [46] Ke C., Yang C., Mori T., Wada T., Liu Y., Inoue Y., Catalyticenantiodifferentiating photocyclodimerization of 2-anthracenecarboxylicacid mediated by a non-sensitizing chiralmetallosupramolecular host, Angew. Chem. Int. Ed., 2009, 48,6675-6677.
  • [47] Maeda H., Okumura T., Yoshimi Y., Mizuno K., Asymmetricinduction in an intramolecular
  • [2+2] photocycloaddition withinchirally modified zeolite supercages, Tetrahedron: Asymmetry,2009, 20, 381-384.
  • [48] Kaprinidis N.A., Landis M.S., Turro N.J., Supramolecularcontrol of photochemical enantiomeric induction and radicalpair recombination in zeolites, Tetrahedron Lett., 1997, 38,2609-2612.
  • [49] Sivaguru J., Sunoj R.B., Wada T., Origane Y., Inoue Y.,Ramamurthy V., Enhanced diastereoselectivity via confinement:photoisomerization of 2,3-diphenylcyclopropane-1-carboxylicacid derivatives within zeolites, J. Org. Chem., 2004, 69,6533-6547.
  • [50] Kaanumalle L.S., Sivaguru J., Sunoj R.B., LakshminarasimhanP.H., Chandrasekhar J., Ramamurthy V., Light-inducedgeometric isomerization of 1,2-diphenylcyclopropanesincluded within Y zeolites: role of cation-guest binding, J. Org.Chem., 2002, 67, 8711-8720.
  • [51] Edman J.R., Photorearrangement of benzonorbornadiene, J.Am. Chem. Soc., 1969, 91, 7103-7104.
  • [52] Hahn R.C., Johnson R.P., Effects of a nitro substituent ondi-p-methane rearrangements of benzonorbornadiene and its
  • [3.2.1] homolog, J. Am. Chem. Soc., 1977, 99, 1508-1513.
  • [53] Joy A., Robbins R.J., Pitchumani K., Ramamurthy V., Asymmetricallymodified zeolite as a medium for enantioselectivephotoreactions: Reactions from spin forbidden excited states,Tetrahedron Lett., 1997, 38, 8825-8828.
  • [54] Wada T., Shikimi M., Inoue Y., Lem G., Turro N.J., First photosensitizedenantiodifferentiating isomerization by optically activesensitizer immobilized in zeolite supercages, Chem. Commun.,2001, 2001, 1864-1865.
  • [55] Mizoguchi J.-i., Kawanami Y., Wada T., Kodama K., AnzaiK., Yanagi T., Inoue Y., Enantiodifferentiating photocyclodimerizationof 2-anthracenecarboxylic acid using a chiralN-(2-hydroxymethyl-4-pyrrolidinyl)benzamide template, Org.Lett., 2006, 8, 6051-6054.
  • [56] Kawanami Y., Pace T.C.S., Mizoguchi J.-i., Yanagi T., NishijimaM., Mori T., Wada T., Bohne C., Inoue Y., Supramolecularcomplexation and enantiodifferentiating photocyclodimerizationof 2-anthracenecarboxylic acid with 4-aminoprolinolderivatives as chiral hydrogen-bonding templates, J. Org.Chem., 2009, 74, 7908-7921.
  • [57] Bach T., Bergmann H., Harms K., Enantioselective intramolecular
  • [2+2]-photocycloaddition reactions in solution, Angew.Chem. Int. Ed., 2000, 39, 2302-2304.
  • [58] Bach T., Bergmann H., Brummerhop H., Lewis W., Harms K., The
  • [2+2]-photocycloaddition of aromatic aldehydes and ketones to3,4-dihydro-2-pyridones: regioselectivity, diastereoselectivity,and reductive ring opening of the product oxetanes, Chem. Eur.J., 2001, 7, 4512-4521.
  • [59] Bach T., Bergmann H., Grosch B., Harms K., Highlyenantioselective intra- and intermolecular
  • [2+2]photocycloaddition reactions of 2-quinolones mediatedby a chiral lactam host: host-guest interactions, productconfiguration, and the origin of the stereoselectivity insolution, J. Am. Chem. Soc., 2002, 124, 7982-7983.
  • [60] Inoue Y., Synthetic chemistry: Light on chirality, Nature, 2005,436, 1099-1100.
  • [61] Bauer A., Westkaemper F., Grimme S., Bach T., Catalytic enantioselectivereactions driven by photoinduced electron transfer,Nature, 2005, 436, 1139-1140.
  • [62] Müller C., Bauer A., Maturi M.M., Cuquerella M.C., MirandaM.A., Bach T., Enantioselective intramolecular
  • [2+2]-photocycloadditionreactions of 4-substituted quinolones catalyzed bya chiral sensitizer with a hydrogen-bonding motif, J. Am. Chem.Soc., 2011, 133, 16689-16697.
  • [63] Mueller C., Bauer A., Bach T., Light-driven enantioselectiveorganocatalysis, Angew. Chem. Int. Ed., 2009, 48, 6640-6642.
  • [64] Vallavoju N., Selvakumar S., Jockusch S., Sibi M.P., Sivaguru J.,Enantioselective organo‐photocatalysis mediated by atropisomericthiourea derivatives, Angew. Chem. Int. Ed., 2014, 53,5604-5608.
  • [65] Narayanam J.M., Stephenson C.R., Visible light photoredoxcatalysis: applications in organic synthesis, Chem. Soc. Rev. ,2011, 40, 102-113.
  • [66] Prier C.K., Rankic D.A., MacMillan D.W., Visible light photoredoxcatalysis with transition metal complexes: applications inorganic synthesis, Chem. Rev. , 2013, 113, 5322-5363.
  • [67] Braun I., Rudroff F., Mihovilovic M.D., Bach T., Synthesis ofenantiomerically pure bicyclo
  • [4.2.0]octanes by Cu-catalyzed
  • [2+2] photocycloaddition and enantiotopos-differentiating ringopening, Angew. Chem. Int. Ed., 2006, 45, 5541-5543.
  • [68] Langer K., Mattay J., Stereoselective intramolecular copper(I)-catalyzed
  • [2+2]- photocycloadditions. enantioselectivesynthesis of (+)- and (-)-grandisol, J. Org. Chem., 1995, 60,7256-7266.
  • [69] Du J., Skubi K.L., Schultz D.M., Yoon T.P., A Dual-CatalysisApproach to Enantioselective
  • [2 + 2] PhotocycloadditionsUsing Visible Light, Science, 2014, 344, 392-396.
  • [70] Huo H., Shen X., Wang C., Zhang L., Röse P., Chen L.-A., HarmsK., Marsch M., Hilt G., Meggers E., Asymmetric photoredoxtransition-metal catalysis activated by visible light, Nature,2014, 515, 100-103.
  • [71] Fukuhara G., Imai M., Yang C., Mori T., Inoue Y., Enantiodifferentiatingphotoisomerization of (Z,Z)-1,3-cyclooctadieneincluded and sensitized by naphthoyl-curdlan, Org. Lett., 2011,1856-1859.
  • [72] Xiao D., Wada T., Inoue Y., Supramolecular enantiodifferentiatingphotoisomerization of (Z)-cyclooctene in lyotropic andthermotropic liquid crystals, Chirality, 2008, 21, 110-113.
  • [73] Brimioulle R., Bach T., Enantioselective Lewis acid catalysisof intramolecular enone
  • [2+2] photocycloaddition reactions,Science, 2013, 342, 840-843.
  • [74] Arceo E., Jurberg I.D., Álvarez-Fernández A., Melchiorre P.,Photochemical activity of a key donor–acceptor complex candrive stereoselective catalytic a-alkylation of aldehydes, NatureChem., 2013, 5, 750-756.

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