Abstract
Asymmetric synthesis constitutes one of the most important areas in synthetic organic chemistry. The selective generation of the desired enantiomer during a reaction gratifies many principles of the “green chemistry”. It makes the reaction more atom economical and avoids the use of unnecessary derivatizations using chiral auxiliaries. The need of resolution techniques could also be eliminated. The merging of visible light catalysis with the asymmetric synthesis has made it more efficient in terms of enantiomeric enrichment. In this chapter, we summarize the recent developments reported in the area of transition metal-free visible light-catalyzed asymmetric synthesis.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Similar content being viewed by others
References
(a) Noyori R (2002) Asymmetric catalysis: science and opportunities (Nobel lecture). Angew Chem Int Ed 41:2008–2022; (b) Knowles WS (2002) Asymmetric hydrogenations (Nobel lecture). Angew Chem Int Ed 41:1998–2007; (c) Sharpless KB (2002) Searching for new reactivity (Nobel lecture). Angew Chem Int Ed 41:2024–2032
Brimioulle R, Lenhart D, Maturi MM, Bach T (2015) Enantioselective catalysis of photochemical reactions. Angew Chem Int Ed 54:3872–3890
Kim J-I, Schuster GB (1990) Enantioselective catalysis of the triplex Diels-Alder reaction: addition of trans-.beta.-methylstyrene to 1,3-cyclohexadiene photosensitized with (-)-1,1’-bis(2,4-dicyanonaphthalene). J Am Chem Soc 112:9635–9637
Ibrahem I, Zhao G-L, Sunden H, Cordova A (2006) A route to 1,2-diols by enantioselective organocatalytic α-oxidation with molecular oxygen. Tetrahedron Lett 47:4659–4663
Rono LJ, Yayla HG, Wang DY, Armstrong MF, Knowles RR (2013) Enantioselective photoredox catalysis enabled by proton-coupled electron transfer: development of an asymmetric aza-pinacol cyclization. J Am Chem Soc 135:17735–17738
Welin ER, Warkentin AA, Conrad JC, MacMillan DWC (2015) Enantioselective α-alkylation of aldehydes by photoredox organocatalysis: rapid access to pharmacophore fragments from β-cyanoaldehydes. Angew Chem Int Ed 54:9668–9672
Hammond GS, Cole RS (1965) Asymmetric induction during energy transfer. J Am Chem Soc 87:3256–3257
Inoue Y, Yokoyama T, Yamasaki N, Tai A (1989) An optical yield that increases with temperature in a photochemically induced enantiomeric isomerization. Nature 341:225–226
Asaoka S, Kitazawa T, Wada T, Inoue Y (1999) Enantiodifferentiating anti-Markovnikov photoaddition of alcohols to 1,1-diphenylalkenes sensitized by chiral naphthalenecarboxylates. J Am Chem Soc 121:8486–8498
Kim J-I, Schuster GB (1992) Enantioselective catalysis of the triplex Diels-Alder reaction: a study of scope and mechanism. J Am Chem Soc 114:9309–9317
Lu R, Yang C, Cao Y, Wang Z, Wada T, Jiao W, Mori T, Inoue Y (2008) Supramolecular enantiodifferentiating photoisomerization of cyclooctene with modified β-cyclodextrins: critical control by a host structure. Chem Commun 374–376
Müller C, Bauer A, Bach T (2009) Light-driven enantioselective organocatalysis. Angew Chem Int Ed 48:6640–6642
Alonso R, Bach T (2014) A chiral thioxanthone as an organocatalyst for enantioselective [2+2] photocycloaddition reactions induced by visible light. Angew Chem Int Ed 53:4368–4371
Neumann M, ldner SF, Kçnig B, Zeitler K (2011) Metal‐free, cooperative asymmetric organophotoredox catalysis with visible light. Angew Chem Int Ed 50:951–954; Angew Chem 123:981–985
Henin F, Muzart J, Pete J-P, M’boungou-M’passi A, Rau H (1991) Enantioselective protonation of a simple enol: aminoalcohol-catalyzed ketonization of a photochemically produced 2-methylinden-3-ol. Angew Chem Int Ed 30:416–418
Cecere G, Kçnig CM, Alleva JL, MacMillan DWC (2013) Enantioselective direct α-amination of aldehydes via a photoredox mechanism: a strategy for asymmetric amine fragment coupling. J Am Chem Soc 135:11521–11524
Vignola N, List B (2004) Catalytic asymmetric intramolecular α-alkylation of aldehydes. J Am Chem Soc 126:450–451; Hayashi Y, Gotoh H, Hayashi T, Shoji M (2005) Diphenylprolinol silyl ethers as efficient organocatalysts for the asymmetric Michael reaction of aldehydes and nitroalkenes. Angew Chem Int Ed 44:4212–4215; Angew Chem 117:4284–4287
Brunner H, Bgler J, Nuber B (1995) Enantioselective catalysis 98. Preparation of 9-amino(9-deoxy)cinchona alkaloids. Tetrahedron Asymmetry 6:1699–1702
Córdova A, Sundén H, Engqvist M, Ibrahem I, Casas J (2004) The direct amino acid-catalyzed asymmetric incorporation of molecular oxygen to organic compounds. J Am Chem Soc 126:8914–8915
Neumann M, Fuldner S, Konig B, Zeitler K (2011) Metal-free, cooperative asymmetric organophotoredox catalysis with visible light. Angew Chem Int Ed 50(4):951–954
Arceo E, Jurberg ID, Alvarez-Fernandez A, Melchiorre P (2013) Photochemical activity of a key donor–acceptor complex can drive stereoselective catalytic α-alkylation of aldehydes. Nat Chem 5:750–756
Bahamonde A, Melchiorre P (2016) Mechanism of the stereoselective α-alkylation of aldehydes driven by the photochemical activity of enamines. J Am Chem Soc 138:8019–8030
Bonilla P, Rey YP, Holden CM, Melchiorre P (2018) Photo-organocatalytic enantioselective radical cascade reactions of unactivated olefins. Angew Chem Int Ed 57:12819–12823
Mazzarella D, Crisenza GEM, Melchiorre P (2018) Asymmetric photocatalytic C−H functionalization of toluene and derivatives. J Am Chem Soc 140:8439–8443
Bergonzini G, Schindler CS, Wallentin C-J, Jacobsen EN, Stephenson CRJ (2014) Photoredox activation and anion binding catalysis in the dual catalytic enantioselective synthesis of β-amino esters. Chem Sci 5:112–116
Lin L, Bai X, Ye X, Zhao X, Tan C-H, Jiang Z (2017) Organocatalytic enantioselective protonation for photoreduction of activated ketones and ketimines induced by visible light. Angew Chem Int Ed 56:13842–13846
Shao T, Yin Y, Lee R, Zhao X, Chai G, Jiang Z (2018) Sequential photoredox catalysis for cascade aerobic decarboxylative povarov and oxidative dehydrogenation reactions of N-aryl a-amino acids. Adv Synth Catal 360:1754–1760
Li J, Kong M, Qiao B, Lee R, Zhao X, Jiang Z (2018) Formal enantioconvergent substitution of alkyl halides via catalytic asymmetric photoredox radical coupling. Nat Commun 9:2445–2453
Liu X, Liu Y, Chai G, Qiao B, Zhao X, Jiang Z (2018) Organocatalytic enantioselective addition of α-aminoalkyl radicals to isoquinolines. Org Lett 20:6298–6301
Bu L, Li J, Yin Y, Qiao B, Chai G, Zhao X, Jiang Z (2018) Organocatalytic asymmetric cascade aerobic oxidation and semipinacol rearrangement reaction: a visible light-induced approach to access chiral 2,2-disubstituted indolin-3-ones. Chem Asian J 13:2382–2387
Yin Y, Dai Y, Jia H, Li J, Bu L, Qiao B, Zhao X, Jiang Z (2018) Conjugate addition-enantioselective protonation of n-aryl glycines to α-branched 2-vinylazaarenes via cooperative photoredox and asymmetric catalysis. J Am Chem Soc 140:6083–6087
Shao T, Li Y, Ma N, Li C, Chai G, Zhao X, Qiao B, Jiang Z (2019) Photoredox-catalyzed enantioselective α-deuteration of azaarenes with D2O. Science 16:410–419
Xiong W, Li S, Fu B, Wang J, Wang Q-A, Yang W (2019) Visible-light induction/Brønsted acid catalysis in relay for the enantioselective synthesis of tetrahydroquinolines. Org Lett 21:4173–4176
Cao K, Tan S, Lee R, Yang S, Jia H, Zhao X, Qiao B, Jiang Z (2019) Catalytic enantioselective addition of prochiral radicals to vinylpyridines. J Am Chem Soc 141:5437–5443
Hou M, Lin L, Chai X, Zhao X, Qiao B, Jiang Z (2019) enantioselective photoredox dehalogenative protonation. Chem Sci 10:6629–6634
Emmanuel MA, Greenberg NR, Oblinsky DG, Hyster TK Accessing non-natural reactivity by irradiating nicotinamide-dependent enzymes with light. Nature 540:414–417
Biegasiewicz KF, Cooper SJ, Emmanuel MA, Miller DC, Hyster TK (2018) Catalytic promiscuity enabled by photoredox catalysis in nicotinamide-dependent oxidoreductases. Nat Chem 10:770–775
Biegasiewicz KF, Cooper SJ, Gao X, Oblinsky DG, Kim JH, Garfinkle SE, Joyce LA, Sandoval BA, Scholes GD, Hyster TK, Photoexcitation of flavoenzymes enables a stereoselective radical cyclization. Science 364:1166–1169.
Zhang W, Fueyo EF, Hollmann F, Martin LL, Pesic M, Wardenga R, Höhne M, Schmidt S (2015) Combining photo-organo redox- and enzyme catalysis facilitates asymmetric C–H bond functionalization. Eur J Org Chem 2019:80–84
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2021 Springer Nature Singapore Pte Ltd.
About this chapter
Cite this chapter
Ujwaldev, S.M., Anilkumar, G. (2021). Visible Light-Catalyzed Asymmetric Synthesis: A Green Perspective. In: Anilkumar, G., Saranya, S. (eds) Green Organic Reactions. Materials Horizons: From Nature to Nanomaterials. Springer, Singapore. https://doi.org/10.1007/978-981-33-6897-2_14
Download citation
DOI: https://doi.org/10.1007/978-981-33-6897-2_14
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-33-6896-5
Online ISBN: 978-981-33-6897-2
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)