Abstract
Green chemistry is developing to invent new reactions that are cheaper, cleaner and use less energy. Acetalization is a common strategy for the protection of aldehydes in synthetic chemistry, yet actual protocols of acetals synthesis are limited by difficult workups, the use of high-loading catalyst, harsh reaction conditions, and catalyst tedious preparation. Alternatively, photocatalysis allows to access functional products with minimum synthetic procedures and waste generation. Here we use sodium 4-[6-(diethylamino)-3-(diethyliminio)-3H-xanthen-9-yl]benzene-1,3-disulfonate (acid red 52) as photocatalyst under yellow light irradiation. We obtained a wide array of acyclic and cyclic acetals in 75–93% yields. Results show the efficient acetalization of aldehydes with alcohols at room temperature, the use of abundant and sustainable alcohols as both the solvents and coupling agents, low catalyst loading, short reaction time, and readily available catalyst, which might be applied to green-catalyzed systems.
Similar content being viewed by others
References
Barbasiewicz M, Maükosza M (2006) Intermolecular reactions of chlorohydrine anions: acetalization of carbonyl compounds under basic conditions. Org Lett 8:3745–3748. https://doi.org/10.1021/ol0613113
Bartlett PA, Johnson WS, Elliott JD (1983) Asymmetric synthesis via acetal templates. 3. On the stereochemistry observed in the cyclization of chiral acetals of polyolefinic aldehydes: formation of optically active homoallylic alcohols. J Am Chem Soc 105:2088–2089. https://doi.org/10.1021/ja00345a082
Chen JR, Hu XQ, Lu LQ, Xiao WJ (2016) Visible light photoredox-controlled reactions of N-radicals and radical ions. Chem Soc Rev 45:2044–2056. https://doi.org/10.1039/C5CS00655D
Darabi HR, Aghapoor K, FarahaniAD MF (2012) Vitamin B1 as a metal-free organocatalyst for greener Paal-Knorr pyrrole synthesis. Environ Chem Lett 10:369–375. https://doi.org/10.1007/s10311-012-0361-7
De Lijser HJP, Rangel NA (2004) Photochemical acetalization of carbonyl compounds in protic media using an in situ generated photocatalyst. J Org Chem 69:8315–8322. https://doi.org/10.1021/jo0485886
Dhakshinamoorthy A, Alvaro M, Garcia H (2010) Metal organic frameworks as solid acid ctalysts for acetalization of aldehydes with methanol. Adv Synth Catal 352:3022–3030. https://doi.org/10.1002/adsc.201000537
Dong J, Yu L, Xie J (2018) A simple and versatile method for the formation of acetals/ketals using trace conventional acids. ACS Omega 3:4974–4985. https://doi.org/10.1021/acsomega.8b00159
Grabowski J, Granda JM, Jurczak J (2018) Preparation of acetals from aldehydes and alcohols under basic conditions. Org Biomol Chem 16:3114–3120. https://doi.org/10.1039/C8OB00017D
Greeves CN, Stuart W (2012) Chemoselectivity and protecting groups Organic chemistry, 2nd edn. Academic press, Oxford University Press, pp 528–561
Gregg BT, Golden KC, Quinn JF (2009) Indium(III)Trifluoromethanesulfonate as an efficient catalyst for the deprotection of acetals and ketals. J Org Chem 72:5890–5893. https://doi.org/10.1021/jo0707075
Gupta P, Mahajan A (2019) Sustainable approaches for steroid synthesis. Environ Chem Lett 17:879–895. https://doi.org/10.1007/s10311-018-00845-x
Hameedv AMA (2018) Efficient synthesis of pyrano[2,3-b] pyridine derivatives using microwave or solar energy. Environ Chem Lett 16:1423–1427. https://doi.org/10.1007/s10311-018-0744-5
Jin J, MacMillan DWC (2015) Alcohols as alkylating agents in heteroarene C-H functionalization. Nature 525:87–90. https://doi.org/10.1038/nature14885
Karimi B, Ebrahimian GR, Seradj H (1999) Efficient and chemoselective conversion of carbonyl compounds to 1,3-dioxanes catalyzed with N-bromosuccinimide under almost neutral reaction conditions. Org Lett. https://doi.org/10.1021/ol0613113
Li Z, Ma P, Tan Y, Liu Y, Gao M, Zhang Y, Yang B, Huang X, Gao Y, Zhang J (2020) Photocatalyst- and transition-metal-free α-allylation of N-aryl tetrahydroisoquinolines mediated by visible light. Green Chem 22:646–650. https://doi.org/10.1039/C9GC04191E
Liu H, Wang Y, Li H, Wang Z, Xu D (2013) Luminescent rhodamine B doped core–shell silica nanoparticle labels for protein microarray detection. Dyes Pigments 98:119–124. https://doi.org/10.1016/j.dyepig.2013.01.027
Mori A, Yamamoto H (1985) Resolution of ketones via chiral acetals. kinetic approach. J Org Chem 50:5444–5446. https://doi.org/10.1021/jo00225a108
Narayanam JMR, Stephenson CRJ (2011) Visible light photoredox catalysis: applications in organic synthesis. Chem Soc Rev 40:102–113. https://doi.org/10.1039/B913880N
Nikitas NF, Triandafillidi I, Kokotos CG (2019) Photo-organocatalytic synthesis of acetals from aldehydes. Green Chem 21:669–674. https://doi.org/10.1039/C8GC03605E
Oates RP, Jones PB (2008) Photosensitized tetrahydropyran transfer. J Org Chem 73:4743–4745. https://doi.org/10.1021/jo800519h
Paprocki D, Wilk M, Madej A, Walde P, Ostaszewski R (2019) Catalyst-free synthesis of α-acyloxycarboxamides in aqueous media. Environ Chem Lett 17:1011–1016. https://doi.org/10.1007/s10311-018-0797-5
Paprocki D, Berłożecki S, Ostaszewski R (2020) Environmental-friendly one-pot cascade synthesis of 3-cyanopiperidin-2,6-diones. Environ Chem Lett 18:165–170. https://doi.org/10.1007/s10311-019-00915-8
Phadtare SB, Shankarling GS (2012) Greener coumarin synthesis by Knoevenagel condensation using biodegradable choline chloride. Environ Chem Lett 10:363–368. https://doi.org/10.1007/s10311-012-0360-8
Procuranti B, Connon SJ (2008) Unexpected catalysis: aprotic pyridinium ions as active and recyclable bronsted acid catalysts in protic media. Org Lett 10:4935–4938. https://doi.org/10.1021/ol802008m
Romero NA, Nicewicz DA (2016) Organic photoredox catalysis. Chem Rev 116:10075–10166. https://doi.org/10.1021/acs.chemrev.6b00057
Shaw MH, Twilton J, MacMillan DWC (2016) Photoredox catalysis in organic tchemistry. J Org Chem 81:6898–6926. https://doi.org/10.1021/acs.joc.6b01449
Sideri IK, Voutyritsa E, Kokotos CG (2018) Org Biomol Chem 16:4596–4614. https://doi.org/10.1039/C8OB00725J
Silva PHR, Gonçalves VLC, Mota CJA (2010) Glycerol acetals as anti-freezing additives for biodiesel. Bioresour Technol 101:6225–6229. https://doi.org/10.1016/j.biortech.2010.02.101
Skubi KL, Blum TR, Yoon TP (2016) Dual catalysis strategies in photochemical synthesis. Chem Rev 116:10035–10074. https://doi.org/10.1021/acs.chemrev.6b00018
Wu S, Duan Z, Hao F, Xiong S, Xiong W, Lv Y, Liu P, Luo H (2017) Preparation of acid-activated sepiolite/rhodamine B@SiO2 hybrid fluorescent pigments with high stability. Dyes Pigment 137:395–402. https://doi.org/10.1016/j.dyepig.2016.10.030
Wuts PGM, Michigan K (2014) Protection for the carbonyl group. Greene’s protective groups in organic synthesis, 5th edn. Academic Press, New York, pp 559–643
Xu G, Cao J, Zhao Y, Zheng L, Tao M, Zhang W (2017) Phosphorylated polyacrylonitrile fibers as an efficient and greener acetalization catalyst. Chem-Asian J 12:2565–2575. https://doi.org/10.1002/asia.201700846
Xu T, Yu Z, Wang L (2009) Iron-promoted cyclization/halogenation of alkynyl diethyl acetals. Org Lett 11:2113–2116. https://doi.org/10.1021/ol9005689
Yi H, Niu L, Wang S, Liu T, Singh AK, Lei A (2017) Visible-light-induced acetalization of aldehydes with alcohols. Org Lett 19:122–125. https://doi.org/10.1021/acs.orglett.6b03403
Zhang K, Chang L, An Q, Wang X, Zuo Z (2019) Dehydroxymethylation of alcohols enabled by cerium photocatalysis. J Am Chem Soc 141:10556–10564. https://doi.org/10.1021/jacs.9b05932
Acknowledgements
We thank the Science Foundation for Young Teachers of Wuyi University (2019td06), the Foundation of the Department of Education of Guangdong Province (2017KZDXM085, 2018KZDXM070).
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Yu, L., Lin, C., Liao, C. et al. Green chemistry: efficient acetalization of aldehydes with alcohols using the acid red 52 photocatalyst. Environ Chem Lett 18, 1353–1359 (2020). https://doi.org/10.1007/s10311-020-00994-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10311-020-00994-y