Pursuit of C–H Borylation Reactions with Non-Precious Heterobimetallic Catalysts: Hypothesis-Driven Variations on a Design Theme

Abstract

This article presents a retrospective account of our group’s heterobinuclear (NHC)Cu-[M_CO] catalyst design concept (NHC = N-heterocyclic carbene, [M_CO] = metal carbonyl anion), the discovery of its application towards UV-light-induced dehydrogenative borylation of unactivated arenes, and the subsequent pursuit of thermal reaction conditions through structural modifications of the catalysts. The account highlights advantages of using a hypothesis-driven catalyst design approach that, while often fruitless with regard to the target transformation in this case, nonetheless vastly expanded the set of heterobinuclear catalysts available for other applications. In other words, curiosity-driven research conducted in a rational manner often provides valuable products with unanticipated applications, even if the primary objective is viewed to have failed.

1 Introduction to Heterobinuclear Catalysts for C–H Borylation

2 Pursuit of Thermal Borylation Conditions

3 Catalysts beyond Copper Carbenes

4 Conclusions

Key words

catalysis - transition metals - copper - iron - tungsten - ­manganese - carbene complexes

• References

• 1 Current address: Intel Corporation.
• 2 Busacca CA, Fandrick DR, Song JJ, Senanayake CH. Adv. Synth. Catal. 2011; 353: 1825
• 3 Torborg C, Beller M. Adv. Synth. Catal. 2009; 351: 3027
• 4 Campos KR, Coleman PJ, Alvarez JC, Dreher SD, Garbaccio RM, Terrett NK, Tillyer RD, Truppo MD, Parmee ER. Science 2019; 363: eaat0805
• 5 Hayler JD, Leahy DK, Simmons EM. Organometallics 2019; 38: 36
• 6 Gildner PG, Colacot TJ. Organometallics 2015; 34: 5497
• 7 Welch GC, Juan RR. S, Masuda JD, Stephan DW. Science 2006; 314: 1124
• 8 Stephan DW, Erker G. Angew. Chem. Int. Ed. 2009; 49: 46
• 9 Stephan DW. Science 2016; 354: aaf7229
• 10 Karunananda MK, Mankad NP. ACS Catal. 2017; 7: 6110
• 11 Allen AE, MacMillan DW. C. Chem. Sci. 2012; 3: 633
• 12 Gade LH. Angew. Chem. Int. Ed. 2000; 39: 2658
• 13 Baranger AM, Bergman RG. J. Am. Chem. Soc. 1994; 116: 3822
• 14 Casey CP, Morris Bullock R. J. Mol. Catal. 1982; 14: 283
• 15 Cooper BG, Napoline JW, Thomas CM. Catal. Rev. 2012; 54: 1
• 16 Pinkes JR, Steffey BD, Vites JC, Cutler AR. Organometallics 1994; 13: 21
• 17 Stephan DW. Coord. Chem. Rev. 1989; 95: 41
• 18 Chapman AM, Haddow MF, Wass DF. J. Am. Chem. Soc. 2011; 133: 18463
• 19 Bauer J, Braunschweig H, Dewhurst RD. Chem. Rev. 2012; 112: 4329
• 20 Schmidt JA. R, Lobkovsky EB, Coates GW. J. Am. Chem. Soc. 2005; 127: 11426
• 21 Mankad NP. Chem. Commun. 2018; 34: 5497
• 22 Pannell KH, Sharma HK. Organometallics 2010; 29: 4741
• 23 Theys R, Dudley M, Hossain M. Coord. Chem. Rev. 2009; 253: 180
• 24 Whitesides GM, Boschetto DJ. J. Am. Chem. Soc. 1969; 91: 4313
• 25 Díez-González S, Nolan S. Synlett 2007; 2158
• 26 Jayarathne U, Mazzacano TJ, Bagherzadeh S, Mankad NP. Organometallics 2013; 32: 3986
• 27 Mazzacano TJ, Mankad NP. J. Am. Chem. Soc. 2013; 135: 17258
• 28 Banerjee S, Karunananda MK, Bagherzadeh S, Jayarathne U, Parmelee SR, Waldhart GW, Mankad NP. Inorg. Chem. 2014; 53: 11307
• 29 King RB. Acc. Chem. Res. 1970; 3: 417
• 30 Morris RH. Chem. Rev. 2016; 116: 8588
• 31 Jayarathne U, Parmelee SR, Mankad NP. Inorg. Chem. 2014; 53: 7730
• 32 Leon NJ, Yu H.-C, Mazzacano TJ, Mankad NP. Polyhedron 2019; 157: 116
• 33 Parmelee SR, Mazzacano TJ, Zhu Y, Mankad NP, Keith JA. ACS Catal. 2015; 5: 3689
• 34 Hartwig JF, Huber S. J. Am. Chem. Soc. 1993; 115: 4908
• 35 Waltz KM, He X, Muhoro C, Hartwig JF. J. Am. Chem. Soc. 1995; 117: 11357
• 36 Waltz KM, Muhoro CN, Hartwig JF. Organometallics 1999; 18: 3383
• 37 Waltz KM, Hartwig JF. Science 1997; 277: 211
• 38 Waltz KM, Hartwig JF. J. Am. Chem. Soc. 2000; 122: 11358
• 39 Hartwig JF. Acc. Chem. Res. 2012; 45: 864
• 40 Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
• 41 Mankad N. Synlett 2014; 25: 1197
• 42 Wang Y, Xie Y, Abraham MY, Wei P, Schaefer HF. III, Schleyer P. vR, Robinson GH. J. Am. Chem. Soc. 2010; 132: 14370
• 43 Mazzacano TJ. Ph.D. Thesis. University of Illinois at Chicago: USA: 2017
• 44 Mankad NP, Laitar DS, Sadighi JP. Organometallics 2004; 23: 3369
• 45 Jordan AJ, Lalic G, Sadighi JP. Chem. Rev. 2016; 116: 8318
• 46 Jordan AJ, Wyss CM, Bacsa J, Sadighi JP. Organometallics 2016; 35: 613
• 47 Frey GD, Donnadieu B, Soleilhavoup M, Bertrand G. Chem. Asian J. 2010; 6: 402
• 48 Romero EA, Olsen PM, Jazzar R, Soleilhavoup M, Gembicky M, Bertrand G. Angew. Chem. 2017; 129: 4082
• 49 Chen H, Hartwig JF. Angew. Chem. Int. Ed. 1999; 38: 3391
• 50 Iverson CN, Smith MR. J. Am. Chem. Soc. 1999; 121: 7696
• 51 Cho J.-Y, Iverson CN, Smith MR. J. Am. Chem. Soc. 2000; 122: 12868
• 52 Chen H, Schlecht S, Semple TC, Hartwig JF. Science 2000; 287: 1995
• 53 Sawyer KR, Cahoon JF, Shanoski JE, Glascoe EA, Kling MF, Schlegel JP, Zoerb MC, Hapke M, Hartwig JF, Webster CE, Harris CB. J. Am. Chem. Soc. 2010; 132: 1848
• 54 Mazzacano TJ, Mankad NP. Chem. Commun. 2015; 51: 5379
• 55 Estes DP, Vannucci AK, Hall AR, Lichtenberger DL, Norton JR. Organometallics 2011; 30: 3444
• 56 Deck PA, Jackson WF, Fronczek FR. Organometallics 1996; 15: 5287
• 57 Liu T, DuBois DL, Bullock RM. Nat. Chem. 2013; 5: 228
• 58 Darmon JM, Raugei S, Liu T, Hulley EB, Weiss CJ, Bullock RM, Helm ML. ACS Catal. 2014; 4: 1246
• 59 Filippou AC, Grünleitner W. Z. Naturforsch. B 1989; 44: 1572
• 60 Ito M, Tejima N, Yamamura M, Endo Yh, Ikariya T. Organometallics 2010; 29: 1886
• 61 Basolo F. Coord. Chem. Rev. 1982; 43: 7
• 62 Karunananda MK, Mankad NP. J. Am. Chem. Soc. 2015; 137: 14598
• 63 Zhang Y, Karunananda MK, Yu H.-C, Clark KJ, Williams W, Mankad NP, Ess DH. ACS Catal. 2019; 9: 2657
• 64 Karunananda MK, Parmelee SR, Waldhart GW, Mankad NP. Organometallics 2015; 34: 3857
• 65 Mazzacano TJ, Leon NJ, Waldhart GW, Mankad NP. Dalton Trans. 2017; 46: 5518
• 66 Levina VA, Rossin A, Belkova NV, Chierotti MR, Epstein LM, Filippov OA, Gobetto R, Gonsalvi L, Lledós A, Shubina ES, Zanobini F, Peruzzini M. Angew. Chem. Int. Ed. 2010; 50: 1367
• 67 Bagherzadeh S, Mankad NP. J. Am. Chem. Soc. 2015; 137: 10898
• 68 Karunananda MK, Mankad NP. Organometallics 2017; 36: 220
• 69 Pye DR, Cheng L.-J, Mankad NP. Chem. Sci. 2017; 8: 4750
• 70 Cheng L.-J, Mankad NP. J. Am. Chem. Soc. 2019; 141: 3710