Microwave-Assisted Aminoalkylation of Phenols via Mustard Carbonate Analogues

Monica Viviano; Giacomo Trapasso; Mattia Annatelli; Ciro Milite; Sabrina Castellano; Fabio Aricò

doi:10.1055/a-1742-3723

Synthesis, Table of Contents

Synthesis 2022; 54(11): 2595-2603
DOI: 10.1055/a-1742-3723

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Microwave-Assisted Aminoalkylation of Phenols via Mustard Carbonate Analogues

Monica Viviano

^aDepartment of Pharmacy, University of Salerno, Via Giovanni Paolo II, 132 - 84084 Fisciano, Salerno, Italy

,

Giacomo Trapasso

^bDepartment of Environmental Sciences Informatics and Statistics, Ca’ Foscari University of Venice, Campus Scientifico, Via Torino 155, 30172 Venezia Mestre, Italy

,

Mattia Annatelli

^bDepartment of Environmental Sciences Informatics and Statistics, Ca’ Foscari University of Venice, Campus Scientifico, Via Torino 155, 30172 Venezia Mestre, Italy

,

Ciro Milite

^aDepartment of Pharmacy, University of Salerno, Via Giovanni Paolo II, 132 - 84084 Fisciano, Salerno, Italy

,

Sabrina Castellano

^aDepartment of Pharmacy, University of Salerno, Via Giovanni Paolo II, 132 - 84084 Fisciano, Salerno, Italy

,

Fabio Aricò ∗

^bDepartment of Environmental Sciences Informatics and Statistics, Ca’ Foscari University of Venice, Campus Scientifico, Via Torino 155, 30172 Venezia Mestre, Italy

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Abstract

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Abstract

A microwave-assisted chlorine-free direct phenol substitution is presented, which is indicated as a key green chemistry research area for pharmaceuticals manufacturers. The reaction of β-aminocarbonates (mustard carbonates) with several substituted phenols in the presence of a polar solvent (acetonitrile or butanol) led to the related aminoalkylated products via the anchimeric assistance of the nitrogen incorporated in the organic carbonate backbone. The aminoalkylation required short reaction time (7 min) and the related products were isolated in high yields (>90%) via quick liquid-liquid extraction or column chromatography depending on the solvent employed. Furthermore, microwave irradiation also promoted the one-pot aminoalkylation of phenol in excellent yield. In this approach a β-aminoalcohol was reacted with phenol in the presence of diethyl carbonate, used for the in situ formation β-aminocarbonate, key intermediate in the consequent anchimerically driven alkylation. The resulting product, namely N,N-dimethyl-2-phenoxyethanamine, was isolated as pure in almost quantitative yield.

Key words

alkylation - green chemistry - phenols - neighboring group effects - dialkyl carbonate - microwave chemistry

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References

References

1a Wang Q.-Q, Begum RA, Day VW, Bowman-James K. Org. Biomol. Chem. 2012; 10: 8786
1b Tang FR, Loke WK. Crit. Rev. Toxicol. 2012; 42: 688
1c Ghabili K, Ansarin K, Shoja MM, Agutter PS, Ghanei M. J. Appl. Toxicol. 2010; 7: 627
1d Jackson KE. Chem. Rev. 1934; 15: 425
1e Malhotra RC, Ganesan K, Sugendran K, Swamy RV. Def. Sci. J. 1999; 49: 9

2a Wilen SH, Delguzzo L, Saferstein R. Tetrahedron 1987; 43: 5089
2b Francl MM, Hansell G, Patel BP, Swindell CS. J. Am. Chem. Soc. 1990; 11: 3535
2c Smith MB, March S. March’s Advanced Organic Chemistry, 6th ed. Wiley; Hoboken: 2007: 446

3 Barkhash VA. Top. Curr. Chem. 1984; 116-117: 1

4a Wang Q.-Q, Ara Begum R, Day VW, Bowman-James K. Inorg. Chem. 2012; 51: 760
4b Choi J.-H, Schloerer NE, Berger J, Prechtl MH. Dalton Trans. 2014; 43: 290
4c Sharghi H, Nasseri MA, Niknam K. J. Org. Chem. 2001; 66: 7287

5a Bermejo JF, Ortega P, Chonco L, Eritja R, Samaniego R, Müllner M, de Jesus E, de la Mata FJ, Flores JC, Gomez R, MuÇoz-Fernandez A. Chem. Eur. J. 2007; 13: 483
5b Liu B, Yu WL, Lai YH, Huang W. Macromolecules 2002; 35: 4975
5c Fan QL, Zhou Y, Lu XM, Hou XY, Huang W. Macromolecules 2005; 38: 2927
5d Breitenkamp RB, Tew GN. Macromolecules 2007; 34: 1163
5e Li J, Meng J, Huang X, Cheng Y, Zhu C. Polymer 2010; 51: 3425

6 Chabner B, Roberts T. Nat. Rev. Cancer 2005; 5: 65
7 Tundo P, Musolino M, Aricò F. Green Chem. 2018; 20: 28

8a Aricò F, Chiurato M, Peltier J, Tundo P. Eur. J. Org. Chem. 2012; 3223
8b Trapasso G, Salaris C, Reich M, Logunova E, Salata C, Kümmerer K, Figoli A, Aricò F. Sustainable Chem. Pharm. 2022; 26: 100639

9a Aricò F, Evaristo S, Tundo P. ACS Sustainable Chem. Eng. 2013; 1: 1319
9b Aricò F, Evaristo S, Tundo P. RSC Adv. 2014; 4: 31071
9c Aricò F, Aldoshin AS, Tundo P. ACS Sustainable Chem. Eng. 2016; 4: 2843
9d Aricò F, Tundo P. Pure Appl. Chem. 2016; 88: 3
9e Aricò F, Udrea I, Crisma M, Tundo P. ChemPlusChem 2015; 80: 471
9f Venkataraman S, Ng VW. L, Coady DJ, Horn HW, Jones GO, Fung TS, Sardon H, Waymouth RM, Hedrick JL, Yang YY. J. Am. Chem. Soc. 2015; 137: 13851

10 Aricò F, Aldoshin AS, Musolino M, Crisma M, Tundo P. J. Org. Chem. 2018; 83: 236
11 Annatelli M, Trapasso G, Salaris C, Salata C, Castellano S, Aricò F. Eur. J. Org. Chem. 2021; 3459
12 Bryan MC, Dunn PJ, Entwistle D, Gallou F, Koenig SG, Hayler JD, Hickey MR, Hughes S, Kopach ME, Moine G, Richardson P, Roschangar F, Steven A, Weiberth FJ. Green Chem. 2018; 20: 5082
13 Bleicher K, Böhm HJ, Müller K, Alanine AI. Nat. Rev. Drug Discov. 2003; 2: 369
14 Kappe C, Dallinger D. Nat. Rev. Drug. Discov. 2006; 5: 51
15 Reichardt C, Welton T. Solvents and Solvent Effects in Organic Chemistry, 4th ed. Wiley-VCH; Weinheim: 2011
16 Aycock DF. Org. Process Res. Dev. 2007; 11: 156

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