ortho- and meta-Selective C–H Activation and Borylation of Aromatic Aldehydes via in situ Generated Imines

Abstract

A ligand-controlled discovery of ortho and meta C–H boryl­ation of aromatic aldehydes is described. In both cases, an amine is used and it was proposed that ortho borylation could be realized using tert-butylamine as the traceless protecting/directing group and meta boryl­ation undergoes via an electrostatic interaction and a secondary interaction between the ligand of the iridium catalyst and the substrate. Remarkably, these electrostatic interactions and secondary B–N interactions offer a unique and unprecedented guiding factor for the meta-selective C–H activation/borylation of benzaldehydes. This is the first example for the C–H activation and functionalization where the ortho and meta position of a substrate has selectively been functionalized, which open a new chapter in electrophilic aromatic substitution chemistry.

1 Introduction

2 C–H Activation and ortho Borylation of Benzaldehydes

3 C–H Activation and meta Borylation of Benzaldehydes

4 Conclusion

Key words

C–H activation - ortho borylation - meta borylation - iridium catalyst - benzaldehyde

• References and Notes

• 1a Johnson JR, Gauerke CG. Org. Synth., Coll. Vol. I 1941; 123
• 1b Bunnet JF, Rauhut MM. Org. Synth., Coll. Vol. IV 1963; 114
• 1c Pearson DE, Pope HW, Hargrove WW. Org. Synth., Coll. Vol. V . John Wiley and Sons; New York: 1971: 117
• 1d Huthmacher K, Effenberger F. Synthesis 1978; 693
• 1e Khan SA, Munawar MA, Siddiq M. J. Org. Chem. 1988; 53: 1799
• 1f Rozen S, Lerman O. J. Org. Chem. 1993; 58: 239
• 1g Eguchi H, Kawaguchi H, Yoshinaga S, Nishida A, Nishiguchi T, Fujisaki S. Bull. Chem. Soc. Jpn. 1994; 67: 1918
• 1h Duan J, Zhang LH, Dolbier WR. Synlett 1999; 1245
• 1i Gelmont M, Oren J. Org. Process Res. Dev. 2002; 6: 591
• 1j Jian H, Tour JM. J. Org. Chem. 2003; 68: 5091
• 1k Okada Y, Yokozawa M, Akiba M, Oishi K, Okawa K, Akeboshi T, Kawamura Y, Inokuma S, Nakamura Y, Nishimura J. Org. Biomol. Chem. 2003; 1: 2506

For selected reviews on C–H bond functionalization, see:
• 2a Jia C, Kitamura T, Fujiwara Y. Acc. Chem. Res. 2001; 34: 633
• 2b Ritleng V, Sirlin C, Pfeffer M. Chem. Rev. 2002; 102: 1731
• 2c Kakiuchi F, Murai S. Acc. Chem. Res. 2002; 35: 826
• 2d Godula K, Sames D. Science 2006; 312: 67
• 2e Diaz-Requejo MM, Perez PJ. Chem. Rev. 2008; 108: 3379
• 2f Chen X, Engle KM, Wang DH, Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094
• 2g Daugulis O, Do HQ, Shabashov D. Acc. Chem. Res. 2009; 42: 1074
• 2h Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
• 2i Colby DA, Bergman RG, Ellman JA. Chem. Rev. 2010; 110: 624
• 2j Cho SH, Kim JY, Kwak J, Chang S. Chem. Soc. Rev. 2011; 40: 5068
• 2k Boorman TC, Larrosa I. Chem. Soc. Rev. 2011; 40: 1910
• 2l Ackermann L. Chem. Rev. 2011; 111: 1315
• 2m Kuhl N, Hopkinson MN, Wencel-Delord J, Glorius F. Angew. Chem. Int. Ed. 2012; 51: 10236
• 3a Matteson DS. Stereodirected Synthesis with Organoboranes. Springer; Berlin: 1995
• 3b Pelter A, Smith K, Brown HC. Borane Reagents. Academic Press; London: 1988
• 4 For leading reviews, see: Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
• 5a Whisler MC, MacNeil S, Snieckus V, Beak P. Angew. Chem. Int. Ed. 2004; 43: 2206
• 5b Hurst TE, Macklin TK, Becker M, Hartmann E, Kügel W, Parisienne-La Salle JC, Batsanov AS, Marder TB, Snieckus V. Chem. Eur. J. 2010; 16: 8155

For a recent review of functional-group-directed borylation, see:
• 6a Ros A, Fernandez R, Lassaletta JM. Chem. Soc. Rev. 2014; 43: 3229
• 6b Preshlock SM, Plattner DA, Maligres PE, Krska SW, Maleczka RE. Jr. Smith M. R. III 2013; 52: 12915
• 6c Paul S, Chotana GA, Holmes D, Reichle RC, Maleczka RE. Jr, Smith MR. III. J. Am. Chem. Soc. 2008; 128: 15552
• 6d Dai H.-X, Yu J.-Q. J. Am. Chem. Soc. 2012; 134: 134
• 6e Kawamorita S, Ohmiya H, Sawamura M. J. Org. Chem. 2010; 75: 3855
• 6f Yamazaki K, Kawamorita S, Ohmiya H, Sawamura M. Org. Lett. 2010; 12: 3978
• 6g Ishiyama T, Isou H, Kikuchi T, Miyaura N. Chem. Commun. 2010; 46: 159
• 6h Kawamorita S, Ohmiya H, Hara K, Fukuoka A, Sawamura M. J. Am. Chem. Soc. 2009; 131: 5058
• 6i Boebel TA, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 7534
• 6j Miyaura N. Bull. Chem. Soc. Jpn. 2008; 81: 1535

For sterically controlled meta borylation, see:
• 7a Cho J.-Y, Tse MK, Holmes D, Maleczka RE. Jr, Smith MR. III. Science 2002; 295: 305
• 7b Ishiyama T, Takagi J, Hartwig JF, Miyaura N. Angew. Chem. Int. Ed. 2002; 41: 3056
• 8 For sterically controlled meta silylation, see: Cheng C, Hartwig JF. Science 2014; 343: 853

For Cu-catalyzed meta arylation, see:
• 9a Phipps RJ, Gaunt MJ. Science 2009; 323: 1595
• 9b Duong HA, Gilligan RE, Cook ML, Phipps RJ, Gaunt MJ. Angew. Chem. Int. Ed. 2011; 50: 463

For mechanistic studies, see:
• 9c Chen B, Hou X.-L, Li Y.-X, Wu Y.-D. J. Am. Chem. Soc. 2011; 133: 7668

For pioneering nitrile-template-directed meta olefination, see:
• 10a Leow D, Li G, Mei T.-S, Yu J.-Q. Nature (London, U.K.) 2012; 486: 518

For mechanistic studies in details, see:
• 10b Yang Y.-F, Cheng G.-J, Liu P, Leow D, Sun T.-Y, Chen P, Zhang X, Yu J.-Q, Wu Y.-D, Houk KN. J. Am. Chem. Soc. 2014; 136: 344
• 10c Cheng G.-J, Yang Y.-F, Liu P, Chen P, Sun T.-Y, Li G, Zhang X, Houk KN, Yu J.-Q, Wu Y.-D. J. Am. Chem. Soc. 2014; 136: 894

For other similar types of examples using nitrile-based template, see:
• 10d Dai H.-X, Li G, Zhang X.-G, Stepan AF, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 7567
• 10e Lee S, Lee H, Tan KL. J. Am. Chem. Soc. 2013; 135: 18778
• 10f Yang G, Lindovska P, Zhu D, Wang P, Tang R.-Y, Movassaghi M, Yu J.-Q. J. Am. Chem. Soc. 2014; 136: 10807
• 10g Tang R.-Y, Li G, Yu J.-Q. Nature (London, U.K.) 2014; 507: 215
• 10h Bera M, Modak A, Patra T, Maji A, Maiti D. Org. Lett. 2014; 16: 5760
• 10i Bera M, Maji A, Sahoo SK, Maiti D. Angew. Chem. Int. Ed. 2015; 54: 8515
• 10j Li S, Ji H, Cai L, Li G. Chem. Sci. 2015; 6: 5595
• 10k Wan Li, Dastbaravardeh N, Li G, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 18056
• 10l Deng Y, Yu J.-Q. Angew. Chem. Int. Ed. 2015; 54: 888
• 10m Li S, Cai L, Ji H, Yang L, Li G. Nat. Commun. 2016; 7: 10443 ; doi: 10.1038/ncomms10443
• 10n Maji A, Bhaskararao B, Singha S, Sunoj RB, Maiti D. Chem. Sci. 2016; 7: 3147

For pyridine nitrogen directed meta functionalization, see:
• 10o Chu L, Shang M, Tanaka K, Chen Q, Pissarnitski N, Streckfuss E, Yu J.-Q. ACS Cent. Sci. 2015; 1: 394

For Ru-catalyzed meta sulfonation and alkylation, see:
• 11a Saidi O, Marafie J, Ledger AE. W, Liu PM, Mahon MF, Kociok-Kohn G, Whittlesey MK, Frost CG. J. Am. Chem. Soc. 2011; 133: 19298
• 11b Hofmann N, Ackermann L. J. Am. Chem. Soc. 2013; 135: 5877
• 11c Paterson AJ, St John-Campbell S, Mahon MF, Press NJ, Frost CG. Chem. Commun. 2015; 51: 12807
• 11d Julià-Hernàndez F, Simonetti M, Larrosa I. Angew. Chem. Int. Ed. 2013; 52: 11458

For meta C–H bromination, see:
• 11e Teskey CJ, Lui AY. W, Greaney MF. Angew. Chem. Int. Ed. 2015; 54: 11677
• 11f Yu Q, Hu L, Wang Y, Zheng S, Huang J. Angew. Chem. Int. Ed. 2015; 54: 15284

For Pd-catalyzed transient mediator employing meta alkylation, see:
• 12a Wang X.-C, Gong W, Fang L.-Z, Zhu R.-Y, Li S, Engle KM, Yu J.-Q. Nature (London, U.K.) 2015; 519: 334
• 12b Dong Z, Wang J, Dong G. J. Am. Chem. Soc. 2015; 137: 5887
• 13 For H-bond directed meta borylation, see: Kuninobu Y, Ida H, Nishi M, Kanai M. Nat. Chem. 2015; 7: 712
• 14 For an electrostatic interaction and a secondary B–N interaction directed meta borylation, see: Bisht R, Chattopadhyay B. J. Am. Chem. Soc. 2016; 138: 84
• 15 Maleczka RE. Jr. Science 2009; 323: 1572

For Ir-catalyzed nitrogen-directed ortho borylation, see:
• 16a Ros A, Estepa B, López-Rodríguez R, Alvarez E, Fernández R, Lassaletta JM. Angew. Chem. Int. Ed. 2011; 50: 11724
• 16b López-Rodríguez R, Ros A, Fernández R, Lassaletta JM. J. Org. Chem. 2012; 77: 9915
• 16c Ros A, López-Rodríguez R, Estepa B, Àlvarez E, Fernández R, Lassaletta JM. J. Am. Chem. Soc. 2012; 134: 4573
• 17 For Rh-catalyzed nitrogen-directed ortho borylation, see: Kawamorita S, Miyazaki T, Ohmiya H, Iwai T, Sawamura M. J. Am. Chem. Soc. 2011; 133: 19310
• 18 For aromatic imine-directed ortho borylation, see: Sasaki I, Amou T, Ito H, Ishiyama T. Org. Biomol. Chem. 2014; 12: 2041

For imine-directed ortho silylation, see:
• 19a Choi G, Tsurugi H, Mashima K. J. Am. Chem. Soc. 2013; 135: 13149
• 19b Williams NA, Uchimaru Y, Tanaka M. Dalton Trans. 2003; 236
• 20 For sterically directed borylation and effect of substituent, see: Chotana GA, Rak MA, Smith MR. III. J. Am. Chem. Soc. 2005; 127: 10539
• 21 Roering AJ, Hale LV. A, Aquier PA, Ringgold MA, Wiederspan ER, Clark TB. Org. Lett. 2012; 14: 3558
• 22a Tamura H, Yamazaki H, Sato H, Sakaki S. J. Am. Chem. Soc. 2003; 125: 16114
• 22b Boller TM, Murphy JM, Hapke M, Ishiyama T, Miyaura N, Hartwig JF. J. Am. Chem. Soc. 2005; 127: 14263
• 23a Das S, Incarito CD, Crabtree RH, Brudvig GW. Science 2006; 312: 1941
• 23b Leung DH, Bergman RG, Raymond KN. J. Am. Chem. Soc. 2006; 128: 9781
• 23c Breslow R, Zhang X, Huang Y. J. Am. Chem. Soc. 1997; 119: 4535
• 24 For encapsulation of iridium species, which is facilitated via an electrostatic interaction, see ref. 23b. The detailed mechanism for the meta C–H activation and borylation will be reported in due course.
• 25a For example of H-bonding of imine, see: Ligtenbarg AG, Hage R, Meetsma A, Feringa BL. J. Chem. Soc., Perkin Trans. 2 1999; 807

For H-bond directed ortho borylation, see:
• 25b Roosen PC, Kallepalli VA, Chattopadhyay B, Singleton DA, Maleczka RE. Jr, Smith MR. III. J. Am. Chem. Soc. 2012; 134: 11350
• 26 Isolation of 3h failed due to the elimination of the Boc group of the substrate during silica gel column chromatography, it was isolated as 3g.