Abstract
The eco-friendly chemistry approach embraces almost all the main branches of chemistry based on the twelve principles introduced by Anastas as green chemistry rules. During the last decade, C–H bond activation protocols attracted intensive consideration as a powerful plan to create organic building blocks of complex structures in organic synthesis and transformations because of its step- and atom-economic nature. In this chapter, a number of innovative green methods of C–H bond activation and functionalization are highlighted.
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References
Hess J, Bednarz D et al (2011) Petroleum and health care: evaluating and managing health care’s vulnerability to petroleum supply shifts. Am J Publ Health 101:1568–1579
(1) Chen K, Baran PS (2009) Total synthesis of eudesmane terpenes by site-selective C–H oxidations. Nature 459:824–828; (2) Jørgensen L, McKerrall SJ et al (2013) 14-step synthesis of (+)-ingenol from (+)-3-carene. Science 341:878–882
Hesp KD, Bergman RG, Ellman JA (2011) Expedient synthesis of N-acyl anthranilamides and β-enamine amides by the Rh (III)-catalyzed amidation of aryl and vinyl C–H bonds with isocyanates. J Am Chem Soc 133:11430–11433
Das P, Dutta A et al (2014) Heterogeneous ditopic ZnFe 2 O 4 catalyzed synthesis of 4 H-pyrans: further conversion to 1, 4-DHPs and report of functional group interconversion from amide to ester. Green Chem 16:1426–1435
Walling C, Jacknow BB (1960) Positive halogen compounds. I. The radical chain halogenation of hydrocarbons by t-butyl hypochlorite1. J Am Chem Soc 82:6108–6112
Davies HML, Du Bois J et al (2011) C–H Functionalization in organic synthesis. Chem Soc Rev 40:1855–1856
Potavathri S, Pereira KC et al (2010) Regioselective oxidative arylation of indoles bearing N-alkyl protecting groups: dual C−H functionalization via a concerted metalation−deprotonation mechanism. Am Chem Soc 132:14676–14681
Blanksby SJ, Ellison GB (2003) Bond dissociation energies of organic molecules. Acc Chem Res 36:255–263
Roudesly F, Oble J, Poli G (2017) Metal-catalyzed CH activation/functionalization: the fundamentals. J Mol Catal a: Chem 426:275–296
Shang R, Ilies L, Nakamura E (2017) Iron-catalyzed C–H bond activation. Chem Rev 117:9086–9139
Li JJ (2015) CH bond activation in organic synthesis. CRC press
(1) Goldman AS, Goldberg KI (2004) Organometallic C–H bond activation: an introduction, ACS; (2) Lapointe D, Fagnou K (2010) Overview of the mechanistic work on the concerted metallation–deprotonation pathway. Chem Lett 39:1118–1126; (3) Ackermann L (2011) Carboxylate-assisted transition-metal-catalyzed C−H bond functionalizations: mechanism and scope. Chem Rev 111:1315–1345; (4) Balcells D, Clot E, Eisenstein O, (2010). C–H bond activation in transition metal species from a computational perspective. Chem Rev 110:749–823; (5) Gallego D, Baquero EA, (2018) Recent advances on mechanistic studies on C–H activation catalyzed by base metals. Open Chem 16: 1001–1058
He J, Wasa M, Chan KS et al (2017) Palladium-catalyzed alkyl C–H bond activation. Chem Rev 117:8754–8786
Park Y, Kim Y et al (2017) Transition metal-catalyzed C–H lamination: scope, mechanism, and applications. Chem Rev 117:9247–9301
Hickman AJ, Sanford MS (2012) High-valent organometallic copper and palladium in catalysis. Nature 484:177–185
Gandeepan P, Müller T et al (2019) 3d transition metals for C–H activation. Chem Rev 119(4):2192–2452
Choy PY, Wong SM et al (2018) Recent developments in palladium-catalysed non-directed coupling of (hetero) arene C–H bonds with C–Z (Z= B, Si, Sn, S, N, C, H) bonds in bi (hetero) aryl synthesis. Org Chem Front 5:288–321
Egorova KS, Ananikov VP (2017) Toxicity of metal compounds: knowledge and myths. Organometallics 36:4071–4090
Gallego D, Baquero EA (2018) Recent advances on mechanistic studies on C–H activation catalyzed by base metals. Open Chem 16:1001–1058
(a) Liu W, Ackermann L (2016) Manganese-catalyzed C–H activation. ACS Catal 6:3743–3752; (b) Shang R, Ilies L, Nakamura E, (2017) Iron-catalyzed C–H bond activation. Chem Rev 117:9086−9139; (c) Wang H, Moselage M et al (2016) Selective synthesis of indoles by cobalt (III)-catalyzed C–H/N–O functionalization with nitrones. ACS Catal 6:2705–2709
Castro LCM, Chatani N (2015) Nickel catalysts/N, N′-bidentate directing groups: an excellent partnership in directed C–H activation reactions. Chem Lett 44:410–421
Daugulis O, Do HQ et al (2009) Palladium-and copper-catalyzed arylation of carbon−hydrogen bonds. Acc Chem Res 42:1074–1086
Shi S, Nawaz KS et al (2018) Advances in enantioselective C–H activation/mizoroki-heck reaction and Suzuki reaction. Catalysts 8:90
Basu D, Kumar S et al (2018) Transition metal catalyzed CH activation for the synthesis of medicinally relevant molecules: a review. J Chem Sci 130:71
Sun CL, Shi ZJ (2014) Transition-metal-free coupling reactions. Chem Rev 114:9219–9280
Gu Y, Wang D (2010) Direct C-3 arylation of N-acetylindoles with anisoles using phenyliodine bis (trifluoroacetate)(PIFA). Tetrahedron Lett 51:2004–2006
Zhang YP, Feng XL (2016) Metal-free, C–H arylation of indole and its derivatives with aryl diazonium salts by visible-light photoredox catalysis. Tetrahedron Lett 57:2298–2302
Morofuji T, Shimizu A et al (2012) Metal-and chemical-oxidant-free C–H/C–H cross-coupling of aromatic compounds: the use of radical-cation pools. Angew Chem Int Ed 51:7259–7262
Kita Y, Tohma H et al (1994) Hypervalent iodine-induced nucleophilic substitution of para-substituted phenol ethers. Generation of cation radicals as reactive intermediates. J Am Chem Soc 116:3684–3691
Eberson L, Hartshorn MP et al (1996) Making radical cations live longer. Chem Commun 18:2105–2112
Kita Y, Takada, et al (1996) Hypervalent iodine reagents in organic synthesis: nucleophilic substitution of p-substituted phenol ethers. Pure Appl Chem 68:627
Ma JJ, Yi WB et al (2015) Transition-metal-free C–H oxidative activation: persulfate-promoted selective benzylic mono-and difluorination. Org Biomol Chem 13:2890–2894
Wang D, Ge B et al (2014) Transition metal-free direct C–H functionalization of quinones and naphthoquinones with diaryliodonium salts: synthesis of aryl naphthoquinones as β-secretase inhibitors. J Org Chem 79:8607–8613
Chen J, Wu J (2017) Transition-metal-free C3 arylation of indoles with aryl halides. Angew Chem Int Ed 56:3951
Shamsabadi A, Chudasama V (2019) Recent advances in metal-free aerobic C–H activation. Org Biomol Chem 17:2865–2872
Jimenez-Gonzalez C, Ponder CS et al (2011) Using the right green yardstick: why process mass intensity is used in the pharmaceutical industry to drive more sustainable processes. Org Process Res Dev 15:912–917
Santoro S, Ferlin F et al (2017) Biomass-derived solvents as effective media for cross-coupling reactions and C–H functionalization processes. Green Chem 19:1601–1612
Fu XP, Liu L et al (2011) “On water”-promoted direct alkynylation of isatins catalyzed by NHC–silver complexes for the efficient synthesis of 3-hydroxy-3-ethynylindolin-2-ones. Green Chem 13:549–553
Fischmeister C, Doucet H (2011) Greener solvents for ruthenium and palladium-catalysed aromatic C–H bond functionalisation. Green Chem 13:741–753
Schäffner B, Schäffner F et al (2010) Organic carbonates as solvents in synthesis and catalysis. Chem Rev 110:4554–4581
Nie R, Lai R et al (2019) Water-mediated C–H activation of arenes with secure carbene precursors: the reaction and its application. Chem Commun 55:11418–11421
Yao C, Qin B et al (2012) One-pot solvent-free synthesis of quinolines by C–H activation/C–C bond formation catalyzed by recyclable iron (III) triflate. RSC Adv 2:3759–3764
Rasina D, Kahler-Quesada A et al (2016) Heterogeneous palladium-catalysed Catellani reaction in biomass-derived γ-valerolactone. Green Chem 18:5025–5030
Sambiagio C, Schönbauer D et al (2018) A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry. Chem Soc Rev 47:6603–6743
Tsurugi H, Yamamoto K et al (2010) Oxidant-free direct coupling of internal alkynes and 2-alkylpyridine via double C−H activations by alkylhafnium complexes. J Am Chem Soc 133:732–735
Hu H, Liu Y et al (2014) Palladium catalyzed oxidative Suzuki coupling reaction of indolizine at the 3-position using oxygen gas as the only oxidant. RSC Adv 4:24389–24393
Tan Y, Yuan W et al (2015) Aerobic Asymmetric dehydrogenative cross-coupling between two C−H groups catalyzed by a chiral-at-metal rhodium complex. Angew Chem Int Ed 54:13045–13048
Matsumoto K, Yoshida M et al (2016) Heterogeneous rhodium-catalyzed aerobic oxidative dehydrogenative cross-coupling: nonsymmetrical biaryl amines. Angew Chem 128:5358
Gaikwad VV, Bhanage BM (2018) Palladium-catalyzed aerobic oxidative carbonylation of C–H bonds in phenols for the synthesis of p-hydroxybenzoates. Eur J Org Chem 22:2877–2881
Rostami A, Khakyzadeh V et al (2018) Co (II)-catalyzed regioselective clean and smooth synthesis of 2-(aryl/alkyl-thio) phenols via sp2 CH bond activation. Molecular Catalysis 452:260–263
Albrecht M (2010) Cyclometalation using d-block transition metals: fundamental aspects and recent trends. Chem Rev 110:576–623
Patra T, Watile R et al (2016) Sequential meta-C–H olefination of synthetically versatile benzyl silanes: effective synthesis of meta-olefinated toluene, benzaldehyde and benzyl alcohols. Chem Commun 52:2027–2203
Herrmann P, Bach T (2011) Diastereotopos-differentiating C–H activation reactions at methylene groups. Chem Soc Rev 40:2022–2038
Yoshida JI, Kataoka K et al (2008) Modern strategies in electroorganic synthesis. Chem Rev 108:2265–2299
Frontana-Uribe BA, Little RD et al (2010) Organic electrosynthesis: a promising green methodology in organic chemistry. Green Chem 12:2099–2119
Cardoso DS, Šljukić B et al (2017) Organic electrosynthesis: from laboratorial practice to industrial applications. Org Process Res Dev 21:1213–1226
Kärkäs MD (2018) Electrochemical strategies for C–H functionalization and C–N bond formation. Chem Soc Rev 47:5786–5865
Meyer TH, Finger LH et al (2019) Trends in Chemistry 1:63–76
Qiu Y, Tian C et al (2018) Electrooxidative ruthenium-catalyzed C−H/O−H annulation by weak O-coordination. Angew Chem Int Ed 57:5818–5822
Song G, Wang F et al (2012) C-C, C–O and C–N bond formation via rhodium (iii)-catalyzed oxidative C–H activation. Chem Soc Rev 41:3651–3678
Qiu Y, Kong WJ et al (2018) Electrooxidative rhodium-catalyzed C−H/C−H activation: electricity as oxidant for cross-dehydrogenative alkenylation. Angew Chem Int Ed 57:5828
Yang QL, Li YQ et al (2017) Palladium-catalyzed C (sp3)−H oxygenation via electrochemical oxidation. J Am Chem Soc 139:3293–3298
Li YQ, Yang QL et al (2017) Palladium-catalyzed C (sp2)–H acetoxylation via electrochemical oxidation. Org Lett 19:2905–2908
Ma C, Zhao CQ et al (2017) Palladium-catalyzed C–H activation/C–C cross-coupling reactions via electrochemistry. Chem Commun 53:12189–12192
Yang QL, Li CZ et al (2018) Palladium-catalyzed electrochemical C–H alkylation of arenes. Organometallics 38:1208–1212
Sauermann N, Meyer TH et al (2017) Electrochemical cobalt-catalyzed C–H oxygenation at room temperature. J Am Chem Soc 139:18452–18455
Tian C, Massignan L et al (2018) Electrochemical C−H/N−H activation by water-tolerant cobalt catalysis at room temperature. Angew Chem Int Ed 57:2383
Tang S, Wang D et al (2018) Cobalt-catalyzed electrooxidative CH/NH [4+2] annulation with ethylene or ethyne. Nat Commun 9:798
Yu Y, Zheng P et al (2018) Electrochemical cobalt-catalyzed C–H or N–H oxidation: a facile route to synthesis of substituted oxindoles. Org Biomol Chem 16:8917–8921
Yang QL, Wang XY et al (2018) Copper-catalyzed electrochemical C–H amination of arenes with secondary amines. J Am Chem Soc 140:11487–11494
Zhang SK, Samanta RC et al (2018) Nickel-catalyzed electrooxidative C−H amination: support for nickel (IV). Chem Eur J 24:19166
Santoro S, Ferlin F et al (2019) C–H functionalization reactions under flow conditions. Chem Soc Rev 48:2767–2782
Gutmann B, Cantillo D et al (2015) Continuous-flow technology—a tool for the safe manufacturing of active pharmaceutical ingredients. Angew Chem Int Ed 54:6688–6728
Mandrelli F, Buco A et al (2017) The scale-up of continuous biphasic liquid/liquid reactions under super-heating conditions: methodology and reactor design. Green Chem 19:1425–1430
Lévesque F, Seeberger PH (2012) Continuous-flow synthesis of the anti-malaria drug artemisinin. Angew Chem Int Ed 51:1706–1709
Su Y, Straathof NJ et al (2014) Photochemical transformations accelerated in continuous-flow reactors: basic concepts and applications. Chem Eur J 20:10562–10589
Vaccaro L, Curini M et al (2018) Definition of green synthetic tools based on safer reaction media, heterogeneous catalysis, and flow technology. Pure Appl Chem 90:21–33
Ferlin F, Santoro S et al (2017) Heterogeneous C–H alkenylations in continuous-flow: oxidative palladium-catalysis in a biomass-derived reaction medium. Green Chem 19:2510–2514
Xu F, Qian XY et al (2017) Synthesis of 4 H-1, 3-benzoxazines via metal-and oxidizing reagent-free aromatic C–H oxygenation. Org Lett 19:6332–6335
Fabry DC, Rueping M (2016) Merging visible light photoredox catalysis with metal catalyzed C–H activations: on the role of oxygen and superoxide ions as oxidants. Acc Chem Res 49:1969–1979
Zeitler K (2009) Photoredoxkatalyse mit sichtbarem Licht. Angew Chem 121:9969–9974
Karkas MD, Porco JA Jr et al (2016) Photochemical approaches to complex chemotypes: applications in natural product synthesis. Chem Rev 116:9683–9747
Ravelli D, Fagnoni M et al (2013) Photoorganocatalysis. What for? Chem Soc Rev 42:97–113
Romero NA, Nicewicz DA (2016) Organic photoredox catalysis. Chem Rev 116:10075–10166
Wang B, Li P et al (2019) Visible-light induced decarboxylative C2-alkylation of benzothiazoles with carboxylic acids under metal-free conditions. Org Biomol Chem 17:115–121
McManus JB, Nicewicz DA (2019) Direct C–H cyanation of arenes via organic photoredox catalysis. J Am Chem Soc 139:2880–2883
Margrey KA, Czaplyski WL et al (2018) A general strategy for aliphatic C–H functionalization enabled by organic photoredox catalysis. J Am Chem Soc 140:4213–4217
Wang GW (2013) Mechanochemical organic synthesis. Chem Soc Rev 42:7668–7700
Cheng H, Hernández JG et al (2017) Mechanochemical ruthenium-catalyzed hydroarylations of alkynes under ball-milling conditions. Org Lett 19:6284–6287
Howard JL, Cao Q et al (2018) Mechanochemistry as an emerging tool for molecular synthesis: what can it offer? Chem Sci 9:3080–3094
Hermann GN, Bolm C (2017) Mechanochemical rhodium (III)-catalyzed C–H bond amidation of arenes with dioxazolones under solventless conditions in a ball mill. ACS Catal 7:4592–4596
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Khakyzadeh, V., Sheikhaleslami, S. (2021). Green Chemistry on C–H Activation. 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_11
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