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DOI: 10.1055/s-0036-1588709
Ion-Pair-Directed meta-Selective C–H Borylation of Aromatic Quaternary Ammonium Salts
Publication History
Received: 06 December 2016
Accepted after revision: 23 January 2017
Publication Date:
13 February 2017 (online)
Abstract
We recently reported the use of ion pairing as a key noncovalent interaction to control regioselectivity in the iridium-catalyzed C–H borylation of aromatic quaternary ammonium salts. Two classes of substrates, benzylamine- and aniline-derived ammonium salts were selectively borylated at the meta position by employing a newly developed anionic ligand for the iridium. It was proposed that the ligand interacts with the cationic substrate via an ion-pairing interaction, positioning the substrate in the optimal orientation for selective activation of the meta C–H bond.
1 Introduction
2 Ion-Pair-Directed meta C–H Borylation
3 Control Experiments
4 Unexpected Selectivity with dtbpy in Cyclohexane
5 Conclusions
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References and Notes
- 1 Mkhalid IA, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2009; 110: 890-890
- 2 Hartwig JF. Chem. Soc. Rev. 2011; 40: 1992-1992
- 3 Roosen PC, Kallepalli VA, Chattopadhyay B, Singleton DA, Maleczka RE, Smith RM. J. Am. Chem. Soc. 2012; 134: 11350-11350
- 4 Boebel TA, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 7534-7534
- 5 Crawford KM, Ramseyer TR, Daley CJ. A, Clark TB. Angew. Chem. Int. Ed. 2014; 53: 7589-7589
- 6 Preshlock SM, Ghaffari B, Maligres PE, Krska SW, Maleczka RE, Smith MR. J. Am. Chem. Soc. 2013; 135: 7572-7572
- 7 Ghaffari B, Preshlock SM, Plattner DL, Staples RJ, Maligres PE, Krska SW, Maleczka RE, Smith MR. J. Am. Chem. Soc. 2014; 136: 14345-14345
- 8 Ishiyama T, Isou H, Kikuchi T, Miyaura N. Chem. Commun. 2010; 46: 159-159
- 9 Kawamorita S, Ohmiya H, Hara K, Fukuoka A, Sawamura M. J. Am. Chem. Soc. 2009; 131: 5058-5058
- 10 Preshlock SM, Plattner DL, Maligres PE, Krska SW, Maleczka RE, Smith MR. Angew. Chem. Int. Ed. 2013; 52: 12915-12915
- 11 Ros A, López-Ródríguez R, Estepa B, Ávarez E, Fernández R, Lassaletta JM. J. Am. Chem. Soc. 2012; 134: 4573-4573
- 12 Bisht R, Chattopadhyay B. J. Am. Chem. Soc. 2016; 138: 84-84
- 13 Kuninobu Y, Ida H, Nishi M, Kanai M. Nat. Chem. 2015; 7: 712-712
- 14 Saito Y, Segawa Y, Itami K. J. Am. Chem. Soc. 2015; 137: 5193-5193
- 15 Ros A, Estepa B, López-Ródríguez R, Ávarez E, Fernández R, Lassaletta JM. Angew. Chem. Int. Ed. 2011; 50: 11724-11724
- 16 Haines BE, Saito Y, Segawa Y, Itami K, Musaev DG. ACS Catal. 2016; 6: 7536-7536
- 17 Doyle AG, Jacobsen EN. Chem. Rev. 2007; 107: 5713-5713
- 18a Brak K, Jacobsen EN. Angew. Chem. Int. Ed. 2013; 52: 534-534
- 18b Mahlau M, List B. Angew. Chem. Int. Ed. 2013; 52: 518-518
- 18c Phipps RJ, Hamilton GL, Toste FD. Nat. Chem. 2012; 4: 603-603
- 18d Shirakawa S, Maruoka K. Angew. Chem. Int. Ed. 2013; 52: 4312-4312
- 18e Hamilton GL, Kang EJ, Mba M, Toste FD. Science 2007; 317: 496-496
- 18f Mukherjee S, List B. J. Am. Chem. Soc. 2007; 129: 11336-11336
- 18g Ohmatsu K, Ito M, Kunieda T, Ooi T. Nat. Chem. 2012; 4: 473-473
- 18h Ohmatsu K, Imagawa N, Ooi T. Nat. Chem. 2014; 6: 47-47
- 19 Dydio P, Reek JN. H. Chem. Sci. 2014; 5: 2135-2135
- 20 Davis HJ, Phipps RJ. Chem. Sci. 2017; 8: 864-864
- 21 Davis HJ, Mihai MT, Phipps RJ. J. Am. Chem. Soc. 2016; 138: 12759-12759
- 22 Takagi J, Sato K, Hartwig JF, Ishiyama T, Miyaura N. Tetrahedron Lett. 2002; 43: 5649-5649
- 23 Sadler SA, Tajuddin H, Mkhalid IA. I, Batsanov AS, Albesa-Jove D, Cheung MS, Maxwell AC, Shukla L, Roberts B, Blakemore DC, Lin Z, Marder TB, Steel PG. Org. Biomol. Chem. 2014; 12: 7318-7318
- 24 See the Supporting Information of ref. 21 for full details of these experiments.