A 1,5-Bifunctional Organomagnesium Reagent for the Synthesis of Disubstituted Anthracenes and Anthrones

Dedicated to Professor Dieter Enders on the occasion of his 70^th birthday

Abstract

The preparation of a 1,5-bifunctional organomagnesium alkoxide reagent by a deprotonation–magnesiation sequence is described. This reagent reacts with carboxylic acid esters to incorporate the carboxyl carbon atom of the ester into the newly formed ring. The magnesium bisalkoxide resulting from this double nucleophilic attack is subsequently transformed in situ into halogenated disubstituted anthracenes, monosubstituted anthracenes, anthrones, or 9-substituted dihydroanthracene-cis-diols by variation of the acidic workup procedures.

Key words

Grignard reactions - organomagnesium reagents - carboxylic acid esters - disubstituted anthracenes - anthrones - acenes

• References

• 1a Fudickar W, Linker T. J. Am. Chem. Soc. 2012; 134: 15071
• 1b Filatov MA, Baluschev S, Landfester K. Chem. Soc. Rev. 2016; 45: 4668
• 1c Zhang G, Yang G, Wang S, Chen Q, Ma JS. Chem. Eur. J. 2007; 13: 3630
• 1d Matsubara Y, Kimura A, Yamaguchi Y, Yoshida Z. Org. Lett. 2008; 10: 5541
• 2 Lu H, Xu B, Dong Y, Chen F, Li Y, Li Z, He J, Li H, Tian W. Langmuir 2010; 26: 6838
• 3 Huang J, Su J.-H, Tian H. J. Mater. Chem. 2012; 22: 10977
• 4a Gray V, Dzebo D, Lundin A, Alborzpour J, Abrahamsson M, Albinsson B, Moth-Poulsen K. J. Mater. Chem. C 2015; 3: 11111
• 4b Ji S, Wu W, Wu W, Guo H, Zhao J. Angew. Chem. Int. Ed. 2011; 50: 1626
• 5a Kotha S, Ghosh AK, Deodhar KD. D. Synthesis 2004; 549
• 5b Hiroki K, Kijima M. Chem. Lett. 2005; 34: 942
• 6 Kaleta J, Dron PI, Zhao K, Shen Y, Císařová I, Rogers CT, Michl J. J. Org. Chem. 2015; 80: 6173
• 7 Zeng B, King SB. Synthesis 2002; 2335
• 8a Yamamoto G, Ōki M. Bull. Chem. Soc. Jpn. 1981; 54: 473
• 8b Reus C, Weidlich S, Bolte M, Lerner H.-W, Wagner M. J. Am. Chem. Soc. 2013; 135: 12892
• 9a Fujiwara Y, Ozawa R, Onuma D, Suzuki K, Yoza K, Kobayashi K. J. Org. Chem. 2013; 78: 2206
• 9b Taylor MS, Swager TM. Org. Lett. 2007; 9: 3695
• 10 Link A, Fischer C, Sparr C. Angew. Chem. Int. Ed. 2015; 54: 12163
• 11 Lotter D, Neuburger M, Rickhaus M, Häussinger D, Sparr C. Angew. Chem. Int. Ed. 2016; 55: 2920

For strategies for magnesium metal activation, see:
• 12a Rieke RD. Acc. Chem. Res. 1977; 10: 301
• 12b Klabunde KJ, Efner HF, Satek L, Donley W. J. Organomet. Chem. 1974; 71: 309
• 12c Kündig EP, Perret C. Helv. Chim. Acta 1981; 64: 2606
• 12d Piller FM, Appukkuttan P, Gavryushin A, Helm M, Knochel P. Angew. Chem. Int. Ed. 2008; 47: 6802
• 12e Shen Z.-L, Knochel P. ACS Catal. 2015; 5: 2324

For a second general preparation of Grignard reagents, see:
• 12f Knochel P, Dohle W, Gommermann N, Kneisel FF, Kopp F, Korn T, Sapountzis I, Vu VA. Angew. Chem. Int. Ed. 2003; 42: 4302
• 12g Krasovskiy A, Straub BF, Knochel P. Angew. Chem. Int. Ed. 2006; 45: 159
• 13 Hercouet A, Le Corre M. Synthesis 1988; 157
• 14 Krasovskiy A, Knochel P. Angew. Chem. Int. Ed. 2004; 43: 3333
• 15 Watson SG, Eastham JF. J. Organomet. Chem. 1967; 9: 165
• 16 Sälinger D, Brückner R. Chem. Eur. J. 2009; 15: 6688
• 17 Kuninobu Y, Tatsuzaki T, Matsuki T, Takai K. J. Org. Chem. 2011; 76: 7005
• 18 Zhang J, Sarrafpour S, Pawle RH, Thomas III SW. Chem. Commun. 2011; 47: 3445
• 19 To SC, Kwong FY. Chem. Commun. 2011; 47: 5079
• 20 Branz SE, Jin K, Liu Y, Dao TN. Org. Prep. Proced. Int. 1992; 24: 127