Abstract
Bioethanol is a major raw chemical produced in large quantities by the fermentation of sugar-containing crops and lignocellulosic materials. As a consequence, there is a need for advanced methods to convert ethanol into fine chemicals. Here, we report the synthesis of higher-order alcohols by cross-coupling of ethanol with primary alcohols under solvent-free conditions, catalyzed by low amounts of a selective manganese pincer complex under mild reaction conditions with a stoichiometric amount of sodium ethoxide. Poisoning experiments suggest that the catalysis system is homogeneous.
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Supporting information for characterization of each synthesized compound is provided including NMR data.
References
Alberico E, Lennox AJJ, Vogt LK et al (2016) Unravelling the mechanism of basic aqueous methanol dehydrogenation catalyzed by Ru–PNP pincer complexes. J Am Chem Soc 138:14890–14904. https://doi.org/10.1021/jacs.6b05692
Alonso F, Riente P, Yus M (2008) Alcohols for the α-alkylation of methyl ketones and indirect Aza-Wittig reaction promoted by nickel nanoparticles. Eur J Org Chem 2008:4908–4914. https://doi.org/10.1002/ejoc.200800729
Alonso DM, Bond JQ, Dumesic JA (2010) Catalytic conversion of biomass to biofuels. Green Chem 12:1493–1513. https://doi.org/10.1039/C004654J
Anbarasan P, Baer ZC, Sreekumar S et al (2012) Integration of chemical catalysis with extractive fermentation to produce fuels. Nature 491:235–239. https://doi.org/10.1038/nature11594
Arevalo R, Chirik PJ (2019) Enabling two-electron pathways with iron and cobalt: from ligand design to catalytic applications. J Am Chem Soc 141:9106–9123. https://doi.org/10.1021/jacs.9b03337
Bähn S, Imm S, Neubert L et al (2011) The catalytic amination of alcohols. ChemCatChem 3:1853–1864. https://doi.org/10.1002/cctc.201100255
Bruneau-Voisine A, Wang D, Dorcet V et al (2017) Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex. J Catal 347:57–62. https://doi.org/10.1016/j.jcat.2017.01.004
Carlini C, Di Girolamo M, Macinai A et al (2003) Selective synthesis of isobutanol by means of the Guerbet reaction: Part 2. Reaction of methanol/ethanol and methanol/ethanol/n-propanol mixtures over copper based/MeONa catalytic systems. J Mol Catal A Chem 200:137–146. https://doi.org/10.1016/S1381-1169(03)00042-6
Chakraborty S, Gellrich U, Diskin-Posner Y et al (2017) Manganese-catalyzed N-formylation of amines by methanol liberating H2: a catalytic and mechanistic study. Angew Chem Int Ed 56:4229–4233. https://doi.org/10.1002/anie.201700681
Choi J, MacArthur AHR, Brookhart M et al (2011) Dehydrogenation and related reactions catalyzed by iridium pincer complexes. Chem Rev 111:1761–1779. https://doi.org/10.1021/cr1003503
Corma A, Navas J, Sabater MJ (2018) Advances in one-pot synthesis through borrowing hydrogen catalysis. Chem Rev 118:1410–1459. https://doi.org/10.1021/acs.chemrev.7b00340
Degering EF, Stoudt T (1951) Polymerization of acetaldehyde and crotonaldehyde catalyzed by aliphatic tertiary amines. J Polym Sci 7:653–656. https://doi.org/10.1002/pol.1951.120070609
Dobereiner GE, Crabtree RH (2010) Dehydrogenation as a substrate-activating strategy in homogeneous transition-metal catalysis. Chem Rev 110:681–703. https://doi.org/10.1021/cr900202j
Dodds DR, Gross RA (2007) Chemicals from biomass. Science 318:1250–1251. https://doi.org/10.1126/science.1146356
Elangovan S, Neumann J, Sortais J-B et al (2016) Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes. Nat Commun 7:12641. https://doi.org/10.1038/ncomms12641
Espinosa-Jalapa NA, Kumar A, Leitus G et al (2017) Synthesis of cyclic imides by acceptorless dehydrogenative coupling of diols and amines catalyzed by a manganese pincer complex. J Am Chem Soc 139:11722–11725. https://doi.org/10.1021/jacs.7b08341
Fu S, Shao Z, Wang Y et al (2017) Manganese-catalyzed upgrading of ethanol into 1-butanol. J Am Chem Soc 139:11941–11948. https://doi.org/10.1021/jacs.7b05939
Furukawa J, Saegusa T, Tsuruta T et al (1959) High polymerization of acetaldehyde by alumina—a new method of preparation of polyether. J Polym Sci 36:546–546. https://doi.org/10.1002/pol.1959.1203613057
Gabriëls D, Hernández WY, Sels B, Van Der Voort P, Verberckmoes A (2015) Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization Catal. Sci Technol 5(3876):3902. https://doi.org/10.1039/C5CY00359H
Guillena G, Ramón DJ, Yus M (2007) Alcohols as electrophiles in C–C bond-forming reactions: the hydrogen autotransfer process. Angew Chem Int Ed 46:2358–2364. https://doi.org/10.1002/anie.200603794
Guillena G, Ramón DJ, Yus M (2010) Hydrogen autotransfer in the N-alkylation of amines and related compounds using alcohols and amines as electrophiles. Chem Rev 110:1611–1641. https://doi.org/10.1021/cr9002159
Gunanathan C, Milstein D (2013) Applications of acceptorless dehydrogenation and related transformations in chemical synthesis. Science 341:1229712. https://doi.org/10.1126/science.1229712
Hamid MHSA, Slatford PA, Williams JMJ (2007) Borrowing hydrogen in the activation of alcohols. Adv Synth Catal 349:1555–1575. https://doi.org/10.1002/adsc.200600638
Huang F, Liu Z, Yu Z (2016) C-Alkylation of ketones and related compounds by alcohols: transition-metal-catalyzed dehydrogenation. Angew Chem Int Ed 55:862–875. https://doi.org/10.1002/anie.201507521
Irrgang T, Kempe R (2019) 3d-metal catalyzed N- and C-alkylation reactions via borrowing hydrogen or hydrogen autotransfer. Chem Rev 119:2524–2549. https://doi.org/10.1021/acs.chemrev.8b00306
Kaloudas D, Pavlova N, Penchovsky R (2021) Lignocellulose, algal biomass, biofuels and biohydrogen: a review. Environ Chem Lett 19:2809–2824. https://doi.org/10.1007/s10311-021-01213-y
Kang Q, Appels L, Tan T et al (2014) Bioethanol from lignocellulosic biomass: current findings determine research priorities. Sci World J 2014:298153. https://doi.org/10.1155/2014/298153
Karimi S, Karri RR, Tavakkoli Yaraki M et al (2021) Processes and separation technologies for the production of fuel-grade bioethanol: a review. Environ Chem Lett 19:2873–2890. https://doi.org/10.1007/s10311-021-01208-9
Kobayashi M, Itoh S, Yoshimura K et al (2020) Iridium complex-catalyzed C2-extension of primary alcohols with ethanol via a hydrogen autotransfer reaction. J Org Chem 85:11952–11958. https://doi.org/10.1021/acs.joc.0c01540
Lator A, Gaillard S, Poater A et al (2018) Well-defined phosphine-free iron-catalyzed N-ethylation and N-methylation of amines with ethanol and methanol. Org Lett 20:5985–5990. https://doi.org/10.1021/acs.orglett.8b02080
Liu Y, Shao Z, Wang Y et al (2019) Manganese-catalyzed selective upgrading of ethanol with methanol into isobutanol. Chemsuschem 12:3069–3072. https://doi.org/10.1002/cssc.201802689
Mastalir M, Glatz M, Gorgas N et al (2016a) Divergent coupling of alcohols and amines catalyzed by isoelectronic hydride MnI and FeII PNP pincer complexes. Chem Eur J 22:12316–12320. https://doi.org/10.1002/chem.201603148
Mastalir M, Glatz M, Pittenauer E et al (2016b) Sustainable synthesis of quinolines and pyrimidines catalyzed by manganese PNP pincer complexes. J Am Chem Soc 138:15543–15546. https://doi.org/10.1021/jacs.6b10433
Mondal A, Sahoo MK, Subaramanian M et al (2020) Manganese(I)-catalyzed sustainable synthesis of quinoxaline and quinazoline derivatives with the liberation of dihydrogen. J Org Chem 85:7181–7191. https://doi.org/10.1021/acs.joc.0c00561
Mukherjee A, Nerush A, Leitus G et al (2016) Manganese-catalyzed environmentally benign dehydrogenative coupling of alcohols and amines to form aldimines and H2: a catalytic and mechanistic study. J Am Chem Soc 138:4298–4301. https://doi.org/10.1021/jacs.5b13519
Nandakumar A, Midya SP, Landge VG et al (2015) Transition-metal-catalyzed hydrogen-transfer annulations: access to heterocyclic scaffolds. Angew Chem Int Ed 54:11022–11034. https://doi.org/10.1002/anie.201503247
Nguyen DH, Trivelli X, Capet F et al (2017) Manganese pincer complexes for the base-free, acceptorless dehydrogenative coupling of alcohols to esters: development, scope, and understanding. ACS Catal 7:2022–2032. https://doi.org/10.1021/acscatal.6b03554
O’Lenick AJ Jr (2001) Guerbet chemistry. Surfactants Deterg 4:311–315. https://doi.org/10.1007/s11743-001-0185-1
Obora Y (2014) Recent advances in α-alkylation reactions using alcohols with hydrogen borrowing methodologies. ACS Catal 4:3972–3981. https://doi.org/10.1021/cs501269d
Osman AI, Mehta N, Elgarahy AM et al (2021) Conversion of biomass to biofuels and life cycle assessment: a review. Environ Chem Lett 19:4075–4118. https://doi.org/10.1007/s10311-021-01273-0
Periyasamy S, Karthik V, Senthil Kumar P et al (2022) Chemical, physical and biological methods to convert lignocellulosic waste into value-added products. A review. Environ Chem Lett 20:1129–1152. https://doi.org/10.1007/s10311-021-01374-w
Shao Z, Wang Y, Liu Y et al (2018) A general and efficient Mn-catalyzed acceptorless dehydrogenative coupling of alcohols with hydroxides into carboxylates. Org Chem Front 5:1248–1256. https://doi.org/10.1039/C8QO00023A
Shao Z, Li Y, Liu C et al (2020) Reversible interconversion between methanol-diamine and diamide for hydrogen storage based on manganese catalyzed (de)hydrogenation. Nat Commun 11:591. https://doi.org/10.1038/s41467-020-14380-3
Shao Z, Yuan S, Li Y et al (2022) Using methanol as a formaldehyde surrogate for sustainable synthesis of N-heterocycles via manganese-catalyzed dehydrogenative cyclization. Chin J Chem 40:1137–1143. https://doi.org/10.1002/cjoc.202100886
Sheehan J, Aden A, Paustian K et al (2003) Energy and environmental aspects of using corn stover for fuel ethanol. J Ind Econ 7:117–146. https://doi.org/10.1162/108819803323059433
Thiyagarajan S, Gunanathan C (2017) Facile Ruthenium(II)-catalyzed α-alkylation of arylmethyl nitriles using alcohols enabled by metal-ligand cooperation. ACS Catal 7:5483–5490. https://doi.org/10.1021/acscatal.7b01427
Vayer M, Morcillo SP, Dupont J et al (2018) Iron-catalyzed reductive ethylation of imines with ethanol. Angew Chem Int Ed 57:3228–3232. https://doi.org/10.1002/anie.201800328
Veibel SN, Nielsen JI (1967) On the mechanism of the guerbet reacrtion. Tetrahedron 23:1723–1733. https://doi.org/10.1016/S0040-4020(01)82571-0
Wang Y, Shao Z, Zhang K et al (2018) Manganese-catalyzed dual-deoxygenative coupling of primary alcohols with 2-Arylethanols. Angew Chem Int Ed 57:15143–15147. https://doi.org/10.1002/anie.201809333
Yang Q, Wang Q, Yu Z (2015) Substitution of alcohols by N-nucleophiles via transition metal-catalyzed dehydrogenation. Chem Soc Rev 44:2305–2329. https://doi.org/10.1039/C4CS00496E
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We thank the top-notch personnel fund of Henan agricultural university (Grant 30501028) for financial support.
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MZ, XL, and XZ performed the optimization and investigated the scope of the substrate. ZS directed the project and wrote the manuscript with input from all authors. All authors analyzed the results and commented on the manuscript.
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Shao, Z., Li, X., Zhang, X. et al. Manganese-catalyzed cross-coupling of primary alcohols with biomass-derived ethanol for upgrading to linear alcohols under solvent-free conditions. Environ Chem Lett 21, 1271–1279 (2023). https://doi.org/10.1007/s10311-023-01578-2
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DOI: https://doi.org/10.1007/s10311-023-01578-2