Chromium-Catalyzed, Regioselective Cross-Coupling of C–O Bonds by Using Organic Bromides as Reactants

Published as part of the Cluster C–O Activation

Abstract

We report a chromium-catalyzed cross-coupling of C–O bonds with widely accessible organic bromides as reactants for the preparation of ortho-arylated or -alkylated aromatic aldehydes at room temperature. The use of metallic magnesium is essential for the reaction to occur, giving it an advantage over previous reactions involving Grignard reagents that have to be prepared separately from organic halides before the coupling.

Key words

chromium - C–O activation - cross-coupling - C–C bond formation - organic bromides - regioselectivity

• References and Notes

• 1 Johansson Seechurn CC. C. Kitching MO. Colacot TJ. Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 5062
• 2 Metal-Catalyzed Cross-Coupling Reactions . 2nd ed; . de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004
• 3 Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals. Vol. 1. Wiley-VCH; Weinheim: 2004
• 4 Wenkert E. Michelotti EL. Swindell CS. J. Am. Chem. Soc. 1979; 101: 2246
• 5 Cornella J. Zarate C. Martin R. Chem. Soc. Rev. 2014; 43: 8081
• 6 Tobisu M. Chatani N. Acc. Chem. Res. 2015; 48: 1717
• 7 Li B.-J. Yu D.-G. Sun C.-L. Shi Z.-J. Chem. Eur. J. 2011; 17: 1728
• 8 Rosen BM. Quasdorf KW. Wilson DA. Zhang N. Resmerita A.-M. Garg NK. Percec V. Chem. Rev. 2011; 111: 1346
• 9 Tobisu M. Chatani N. Top. Organomet. Chem. 2012; 44: 35
• 10 Su B. Cao Z.-C. Shi Z.-J. Acc. Chem. Res. 2015; 48: 886

For selected examples, see:
• 11a Ohtsuki A. Sakurai S. Tobisu M. Chatani N. Chem. Lett. 2016; 45: 1277
• 11b Tobisu M. Takahira T. Morioka T. Chatani N. J. Am. Chem. Soc. 2016; 138: 6711
• 11c Nakamura K. Tobisu M. Chatani N. Org. Lett. 2015; 17: 6142
• 11d Tobisu M. Takahira T. Chatani N. Org. Lett. 2015; 17: 4352
• 11e Tobisu M. Morioka T. Ohtsuki A. Chatani N. Chem. Sci. 2015; 6: 3410
• 11f Morioka T. Nishizawa A. Nakamura K. Tobisu M. Chatani N. Chem. Lett. 2015; 44: 1729
• 11g Tobisu M. Yasutome A. Kinuta H. Nakamura K. Chatani N. Org. Lett. 2014; 16: 5572
• 11h Tobisu M. Yamakawa K. Shimasaki T. Chatani N. Chem. Commun. 2011; 47: 2946
• 11i Tobisu M. Shimasaki T. Chatani N. Chem. Lett. 2009; 38: 710
• 11j Tobisu M. Shimasaki T. Chatani N. Angew. Chem. Int. Ed. 2008; 47: 4866
• 11k Tobisu M. Takahira T. Ohtsuki A. Chatani N. Org. Lett. 2015; 17: 680
• 12 Dankwardt JW. Angew. Chem. Int. Ed. 2004; 43: 2428

For selected examples, see:
• 13a Kondo H. Kochi T. Kakiuchi F. Org. Lett. 2017; 19: 794
• 13b Kondo H. Akiba N. Kochi T. Kakiuchi F. Angew. Chem., Int. Ed. 2015; 54: 9293
• 13c Ogiwara Y. Kochi T. Kakiuchi F. Org. Lett. 2011; 13: 3254
• 13d Ueno S. Mizushima E. Chatani N. Kakiuchi F. J. Am. Chem. Soc. 2006; 128: 16516
• 13e Kakiuchi F. Usui M. Ueno S. Chatani N. Murai S. J. Am. Chem. Soc. 2004; 126: 2706

For selected examples, see:
• 14a Cao Z.-C. Shi Z.-J. J. Am. Chem. Soc. 2017; 139: 6546
• 14b Zhao F. Zhang Y.-F. Wen J. Yu D.-G. Wei J.-B. Xi Z. Shi Z.-J. Org. Lett. 2013; 15: 3230
• 14c Yu D.-G. Wang X. Zhu R.-Y. Luo S. Zhang X.-B. Wang B.-Q. Wang L. Shi Z.-J. J. Am. Chem. Soc. 2012; 134: 14638
• 14d Yu D.-G. Shi Z.-J. Angew. Chem. Int. Ed. 2011; 50: 7097
• 14e Yu D.-G. Yu M. Guan B.-T. Li B.-J. Zheng Y. Wu Z.-H. Shi Z.-J. Org. Lett. 2009; 11: 3374
• 14f Li B.-J. Xu L. Wu Z.-H. Guan B.-T. Sun C.-L. Wang B.-Q. Shi Z.-J. J. Am. Chem. Soc. 2009; 131: 14656
• 14g Guan B.-T. Wang Y. Li B.-J. Yu D.-G. Shi Z.-J. J. Am. Chem. Soc. 2008; 130: 14468
• 14h Guan B.-T. Xiang S.-K. Wang B.-Q. Sun Z.-P. Wang Y. Zhao K.-Q. Shi Z.-J. J. Am. Chem. Soc. 2008; 130: 3268
• 14i Guan B.-T. Xiang S.-K. Wu T. Sun Z.-P. Wang B.-Q. Zhao K.-Q. Shi Z.-J. Chem. Commun. 2008; 1437

For selected examples, see:
• 15a Gu Y. Martin R. Angew. Chem. Int. Ed. 2017; 56: 3187
• 15b Zarate C. Nakajima M. Martin R. J. Am. Chem. Soc. 2017; 139: 1191
• 15c Zarate C. Manzano R. Martin R. J. Am. Chem. Soc. 2015; 137: 6754
• 15d Cornella J. Jackson EP. Martin R. Angew. Chem. Int. Ed. 2015; 54: 4075
• 15e Correa A. Martin R. J. Am. Chem. Soc. 2014; 136: 7253
• 15f Zarate C. Martin R. J. Am. Chem. Soc. 2014; 136: 2236
• 15g Cornella J. Gómez-Bengoa E. Martin R. J. Am. Chem. Soc. 2013; 135: 1997
• 16a Guo L. Liu X. Baumann C. Rueping M. Angew. Chem. Int. Ed. 2016; 55: 15415
• 16b Liu X. Hsiao C.-C. Kalvet I. Leiendecker M. Guo L. Schoenebeck F. Rueping M. Angew. Chem. Int. Ed. 2016; 55: 6093
• 17a Zhao Y. Snieckus V. J. Am. Chem. Soc. 2014; 136: 11224
• 17b Zhao Y. Snieckus V. Org. Lett. 2015; 17: 4674

Rh-catalyzed functionalizations of C–O bonds have been recently disclosed by Chatani and co-workers; see:
• 18a Tobisu M. Yasui K. Aihara Y. Chatani N. Angew. Chem. Int. Ed. 2017; 56: 1877
• 18b Kinuta H. Tobisu M. Chatani N. J. Am. Chem. Soc. 2015; 137: 1593
• 19 Cong X. Tang H. Zeng X. J. Am. Chem. Soc. 2015; 137: 14367
• 20 Cao Z.-C. Luo Q.-Y. Shi Z.-J. Org. Lett. 2016; 18: 5978

For examples of cross-coupling reactions using organic halides as reactants mediated by metallic magnesium, see:
• 21a Czaplik WM. Mayer M. von Wangelin AJ. Angew. Chem. Int. Ed. 2009; 48: 607
• 21b Ilies L. Kobayashi M. Matsumoto A. Yoshikai N. Nakamura E. Adv. Synth. Catal. 2012; 354: 593
• 21c Liu J.-H. Yang C.-T. Lu X.-Y. Zhang Z.-Q. Xu L. Cui M. Lu X. Xiao B. Fu Y. Liu L. Chem. Eur. J. 2014; 20: 15334
• 21d Li Z. Sun H.-M. Shen Q. Org. Biomol. Chem. 2016; 14: 3314
• 22 o-Arylated Arylcarbaldehydes 3a–m; General Procedure A dried Schlenk tube was charged with (o-methoxyaryl)aldimine 1 (0.2 mmol), Mg (11 mg, 0.44 mmol), and CrCl₂ (3 mg, 0.02 mmol). The appropriate aryl bromide 2 (0.4 mmol) was added by a syringe under N₂. THF (2 mL) was then added, and the mixture was stirred at r.t. for 12 h. The reaction was quenched with 3 N HCl (1 mL), and the resulting mixture was stirred at r.t. for another 0.5 h and then extracted with EtOAc (3 × 10 mL). The organic layers were combined, dried (Na₂SO₄), and concentrated under vacuum to give a crude product that was purified by chromatography (silica gel) 1,1′:4′,1′′-Terphenyl-2-carbaldehyde (3b) Prepared by the general procedure from imine 1a (38 mg, 0.2 mmol) and 4-bromobiphenyl (2b). The crude product was purified by column chromatography [silica gel, EtOAc–PE (1:50)] to give a white solid; yield: 39 mg (75%); mp 111–113 °C; IR (neat): 3025, 2961, 2876, 1680, 1594, 1471, 1389, 1250, 1070, 1006, 856, 827 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 10.06 (s, 1 H), 8.04 (d, J = 8.0 Hz, 1 H), 7.71–7.65 (m, 5 H), 7.53–7.45 (m, 6 H), 7.37 (t, J = 7.2 Hz, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 192.6, 145.7, 141.2, 140.4, 136.8, 133.9, 133.8, 130.9, 130.7, 129.1, 128.0, 127.83, 127.82, 127.3.
• 23 Shi Z. Glorius F. Chem. Sci. 2013; 4: 829