Synthesis of Aryl Ethers from Aromatic Carboxylic Acids

Abstract

A silver/copper bimetallic catalyst system promotes the decarboxylative Chan–Evans–Lam alkoxylation of ortho-substituted aromatic carboxylate salts with tetraalkyl orthosilicates or triaryl borates. Non-ortho-substituted carboxylates are alkoxylated via an ortho-C–H-alkoxylation with concomitant cleavage of the carboxylate directing group via protodecarboxylation. This way, meta-substituted carboxylates are converted into para-substituted alkoxyarenes and vice versa. The combined processes provide a convenient synthetic entry to the important class of aromatic ethers from widely available carboxylic acids.

Key words

aryl ethers - C–C activation - C–H activation - C–O bond formation - decarboxylative coupling

• References

• 1a Elias H.-G. An Introduction to Polymer Science . Wiley-VCH; Weinheim: 1997
• 1b Müller F. Agrochemicals . Wiley-VCH; Weinheim: 1999
• 1c Li JJ, Johnson DS, Sliskovic DR, Roth BD. Contemporary Drug Synthesis . Wiley; New York: 2004
• 1d Li JJ, Johnson DS. Modern Drug Synthesis . Wiley; New York: 2010
• 1e Enthaler S, Company A. Chem. Soc. Rev. 2011; 40: 4912
• 2 March J. Advanced Organic Chemistry . Wiley-Interscience; Hoboken: 1992

For reviews, see:
• 3a Hartwig JF. Nature 2008; 455: 314
• 3b Ley SV, Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400 ; Angew. Chem. 2003, 115, 5558
• 4a Chan DM. T, Monaco KL, Wang R.-P, Winters MP. Tetrahedron Lett. 1998; 39: 2933
• 4b Evans DA, Katz JL, West TR. Tetrahedron Lett. 1998; 39: 2937
• 4c Lam PY. S, Clark CG, Saubern S, Adams J, Winters MP, Chan DM. T, Combs A. Tetrahedron Lett. 1998; 39: 2941
• 5 For a review on this topic, see: Qiao JX, Lam PY. S. Synthesis 2011; 829

For reviews on decarboxylative couplings, see:
• 6a Goossen LJ, Rodríguez N, Goossen K. Angew. Chem. Int. Ed. 2008; 47: 3100 ; Angew. Chem. 2008, 120, 3144
• 6b Goossen LJ, Collet F, Goossen K. Isr. J. Chem. 2010; 50: 617
• 6c Rodríguez N, Goossen LJ. Chem. Soc. Rev. 2011; 40: 5030
• 6d Shang R, Liu L. Sci. China Chem. 2011; 54: 1670
• 6e Dzik WI, Lange PP, Goossen LJ. Chem. Sci. 2012; 3: 2671
• 7a Goossen LJ, Deng G, Levy LM. Science 2006; 313: 662
• 7b Goossen LJ, Rodríguez N, Linder C. J. Am. Chem. Soc. 2008; 130: 15248
• 7c Rudolphi F, Song B, Goossen LJ. Adv. Synth. Catal. 2011; 353: 337
• 8 Bhadra S, Dzik WI, Goossen LJ. J. Am. Chem. Soc. 2012; 134: 9938
• 9 Bhadra S, Dzik WI, Goossen LJ. Angew. Chem. Int. Ed. 2013; 52: 2959 ; Angew. Chem. 2013, 125, 3031
• 10 Milton EJ, Fuentes JA, Clarke ML. Org. Biomol. Chem. 2009; 7: 2645
• 11a Goossen LJ, Linder C, Rodríguez N, Lange PP, Fromm A. Chem. Commun. 2009; 7173
• 11b Cornella J, Sanchez C, Banawa D, Larrosa I. Chem. Commun. 2009; 7176
• 11c Goossen LJ, Rodríguez N, Linder C, Lange PP, Fromm A. ChemCatChem 2010; 2: 430
• 12 For an overview on carboxylate directed C–H functionalizations of arenes, see: Satoh T, Miura M. Synthesis 2010; 3395

Examples of carboxylate directed C–H hydroxylations:
• 13a Zhang Y.-H, Yu J.-Q. J. Am. Chem. Soc. 2009; 131: 14654
• 13b Makhlynets OV, Das P, Taktak S, Flook M, Mas-Ballesté R, Rybak-Akimova EV, Que Jr. L. Chem. Eur. J. 2009; 15: 13171
• 14a Goossen LJ, Thiel WR, Rodríguez N, Linder C, Melzer B. Adv. Synth. Catal. 2007; 349: 2241
• 14b Goossen LJ, Manjolinho F, Khan BA. J. Org. Chem. 2009; 74: 2620