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Synthesis
DOI: 10.1055/a-2722-6393
DOI: 10.1055/a-2722-6393
Short Review
Synthesis of Transition-Metal–Boryl Complexes from Diboron Reagents
Authors
Supported by: State Key Laboratory of Synthetic Chemistry
Supported by: Croucher Foundation
Supported by: Chinese University of Hong Kong
Supported by: Research Grants Council of HKSAR 14307424
Funding Information This work is supported by grants from the Research Grants Council of HKSAR (14307424).
Abstract
Transition metal (TM)-catalyzed borylation reactions using diboron reagents have been extensively studied and hold significant value in organic synthesis. As key intermediates in these reactions, TM–boryl complexes have garnered increasing research attention due to their crucial roles in catalytic processes. In this short review, we provide a comprehensive summary of diverse TM–boryl complexes synthesized from diboron reagents, highlighting their structures, reactivities, and roles in catalytic reactions. Additionally, future directions and perspectives for advancing this research field are discussed.
Keywords
TM–boryl complexes - Diboron reagents - Transition metal catalysis - Borylation - OrganometallicsPublication History
Received: 30 July 2025
Accepted after revision: 13 October 2025
Article published online:
06 November 2025
© 2025. Thieme. All rights reserved.
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References
- 1a Smith K. Chem Soc Rev 1974; 3: 443
- 1b Davidson M. Contemporary Boron Chemistry. Vol. 253. 1st ed. Royal Society of Chemistry; 2000
- 1c Ramachandran PV, Brown HC, Goralski CT. et al. Organoboranes for Syntheses. Vol. 783. 1st ed. ACS Publications: 2001
- 1d Ali HA, Dembitsky VM, Srebnik M. Contemporary Aspects of Boron: chemistry and Biological Applications. 1st ed. Elsevier; 2005
- 1e Baker SJ, Ding CZ, Akama T, Zhang Y-K, Hernandez V, Xia Y. Fut Med Chem 2009; 1: 1275
- 1f Suzuki A. Heterocycles 2010; 80: 15
- 1g Cheng F, Jäkle F. Polym Chem 2011; 2: 2122
- 1h Hall DG. Boronic Acids: preparation, Applications in Organic Synthesis and Medicine. 2nd ed. Weinheim: Wiley-VCH; 2011
- 1i Lennox AJ, Lloyd-Jones GC. Chem Soc Rev 2014; 43: 412
- 1j Fernández E, Whiting A. Synthesis and Application of Organoboron Compounds. Vol. 49. 1st ed. Springer; 2015
- 1k Xu L, Zhang S, Li P. Chem Soc Rev 2015; 44: 8848
- 1l Diaz DB, Yudin AK. Nat Chem 2017; 9: 731
- 1m Fyfe JW, Watson A. J Chem 2017; 3: 31
- 1n Ji L, Griesbeck S, Marder TB. Chem Sci 2017; 8: 846
- 1o Aydin M. ed. Recent Advances in Boron-Containing Materials. 1st ed. IntechOpen; 2020
- 1p Huang Z, Wang S, Dewhurst RD, Ignat’ev NV, Finze M, Braunschweig H. Angew Chem Int Ed 2020; 59: 8800
- 1q Marotta A, Adams CE, Molloy JJ. Angew Chem Int Ed 2022; 61: e202207067
- 1r Messner K, Vuong B, Tranmer GK. Pharmaceuticals 2022; 15: 264
- 2a Crudden CM, Edwards D. Eur J Org Chem 2003; 2003: 4695
- 2b Burks HE, Morken JP. Chem Commun 2007; 4717
- 2c Chow WK, Yuen OY, Choy PY. et al. RSC Adv 2013; 3: 12518
- 2d Tsuji Y, Fujihara T. Chem Rec 2016; 16: 2294
- 2e Yoshida H. ACS Catal 2016; 6: 1799
- 2f Obligacion JV, Chirik PJ. Nat Rev Chem 2018; 2: 15
- 2g Guo X, Yang T, Sheong FK, Lin Z. ACS Catal 2021; 11: 5061
- 2h Hu J, Ferger M, Shi Z, Marder TB. Chem Soc Rev 2021; 50: 13129
- 2i Yang X, Ge S. Curr Opin Green Sustainability Chem 2021; 31: 100542
- 2j Geier SJ, Vogels CM, Melanson JA, Westcott SA. Chem Soc Rev 2022; 51: 8877
- 2k Magre M, Szewczyk M, Rueping M. Chem Rev 2022; 122: 8261
- 2l Hassan MMM, Guria S, Dey S, Das J, Chattopadhyay B. Sci Adv 2023; 9: eadg3311
- 2m Li B, Liang H, Vignesh A, Zhou X, Liu Y, Ke Z. Molecules 2023; 28: 2252
- 2n Yu IF, Wilson JW, Hartwig JF. Chem Rev 2023; 123: 11619
- 2o Waltz KM, Hartwig JF. Science 1997; 277: 211
- 2p Iverson CN, Smith III MR. J Am Chem Soc 1999; 121: 7696
- 2q Takahashi K, Ishiyama T, Miyaura N. J Organomet Chem 2001; 625: 47
- 2r Sagawa T, Asano Y, Ozawa F. Organometallics 2002; 21: 5879
- 2s Teltewskoi M, Panetier JA, Macgregor SA, Braun T. Angew Chem Int Ed 2010; 49: 3947
- 2t Yun J. Asian J Org Chem 2013; 2: 1016
- 3a Neeve EC, Geier SJ, Mkhalid IAI, Westcott SA, Marder TB. Chem Rev 2016; 116: 9091
- 3b Bose SK, Mao L, Kuehn L. et al. Chem Rev 2021; 121: 13238
- 3c Iverson CN, Smith III MR. Organometallics 1996; 15: 5155
- 3d Thomas RL, Souza FE, Marder TB. J Chem Soc, Dalton Trans 2001; 1650
- 4a Zhao H, Lin Z, Marder TB. J Am Chem Soc 2006; 128: 15637
- 4b Liu B, Gao M, Dang L, Zhao H, Marder TB, Lin Z. Organometallics 2012; 31: 3410
- 4c Zinser CM, Nahra F, Falivene L. et al. Chem Commun 2019; 55: 6799
- 4d Tao L, Guo X, Li J, Li R, Lin Z, Zhao W. J Am Chem Soc 2020; 142: 18118
- 4e Suzuki A, Guo X, Lin Z, Yamashita M. Chem Sci 2021; 12: 917
- 5a Braunschweig H. Angew Chem Int Ed 1998; 37: 1786
- 5b Irvine GJ, Lesley MJG, Marder TB. et al. Chem Rev 1998; 98: 2685
- 5c Braunschweig H, Colling M. Coord Chem Rev 2001; 223: 1
- 5d Aldridge S, Coombs DL. Coord Chem Rev 2004; 248: 535
- 5e Braunschweig H, Kollann C, Rais D. Angew Chem Int Ed 2006; 45: 5254
- 5f Segawa Y, Yamashita M, Nozaki K. Angew Chem Int Ed 2007; 46: 6710
- 5g Braunschweig H, Dewhurst RD, Schneider A. Chem Rev 2010; 110: 3924
- 5h Kaur U, Saha K, Gayen S, Ghosh S. Coord Chem Rev 2021; 446: 214106
- 5i Cid J, Gulyas H, Carbo JJ, Fernandez E. Chem Soc Rev 2012; 41: 3558
- 5j Gulyás H, Bonet A, Pubill-Ulldemolins C, Solé C, Cid J, Fernández E. Pure Appl Chem 2012; 84: 2219
- 5k Westcott SA, Fernández E. In Adv. Organomet. Chem. Vol. 63. Elsevier; 2015: 39
- 6a Ye Z, Kwok CY, Lam SL, Wu L, Lyu H. J Am Chem Soc 2025; 147: 14915
- 6b Lin J, Zhang P, Lou X, Lin Z, Lyu H, Quan Y. J Am Chem Soc 2025; 147: 18397
- 7 Lin T-P, Peters JC. J Am Chem Soc 2014; 136: 13672
- 9a Giju KT, Bickelhaupt FM, Frenking G. Inorg Chem 2000; 39: 4776
- 9b Dickinson AA, Willock DJ, Calder RJ, Aldridge S. Organometallics 2002; 21: 1146
- 9c Zhu J, Lin Z, Marder TB. Inorg Chem 2005; 44: 9384
- 9d Cid J, Carbó JJ, Fernández E. Chem Eur J 2012; 18: 12794
- 10 Hewes JD, Kreimendahl CW, Marder TB, Hawthorne MF. J Am Chem Soc 1984; 106: 5757
- 11a Baker RT, Ovenall DW, Calabrese JC. et al. J Am Chem Soc 1990; 112: 9399
- 11b Knorr JR, Merola JS. Organometallics 1990; 9: 3008
- 12 Himmel HJ. Eur J Inorg Chem 2025; 2500214
- 13a Burgess K, Van Der Donk WA, Westcott SA, Marder TB, Baker RT, Calabrese JC. J Am Chem Soc 1992; 114: 9350
- 13b Baker RT, Calabrese JC, Westcott SA, Nguyen P, Marder TB. J Am Chem Soc 1993; 115: 4367
- 14a Nguyen P, Lesley G, Taylor NJ. et al. Inorg Chem 1994; 33: 4623
- 14b Dai C, Stringer G, Marder TB, Scott AJ, Clegg W, Norman NC. Inorg Chem 1997; 36: 272
- 14c Clegg W, Lawlor FJ, Marder TB. et al. J Chem Soc, Dalton Trans 1998; 301
- 15 Hartwig JF, Huber S. J Am Chem Soc 1993; 115: 4908
- 16 He X, Hartwig JF. Organometallics 1996; 15: 400
- 17 Bedford RB, Brenner PB, Carter E, Gallagher T, Murphy DM, Pye DR. Organometallics 2014; 33: 5940
- 19 Dai C, Stringer G, Corrigan JF, Taylor NJ, Marder TB, Norman NC. J Organomet Chem 1996; 513: 273
- 20 Adams CJ, Baber RA, Batsanov AS. et al. Dalton Trans 2006; 1370
- 21a Laitar DS, Müller P, Sadighi JP. J Am Chem Soc 2005; 127: 17196
- 21b Dang L, Lin Z, Marder TB. Organometallics 2008; 27: 4443
- 21c Dang L, Zhao H, Lin Z, Marder TB. Organometallics 2008; 27: 1178
- 21d Zhao H, Dang L, Marder TB, Lin Z. J Am Chem Soc 2008; 130: 5586
- 21e Kleeberg C, Dang L, Lin Z, Marder TB. Angew Chem Int Ed 2009; 48: 5350
- 22 Tran BL, Adhikari D, Fan H, Pink M, Mindiola DJ. alton Trans 2010; 39: 358
- 23 Adhikari D, Huffman JC, Mindiola DJ. Chem Commun 2007; 4489
- 24 Drescher W, Schmitt-Monreal D, Jacob CR, Kleeberg C. Organometallics 2020; 39: 538
- 25a Obligacion JV, Semproni SP, Chirik PJ. J Am Chem Soc 2014; 136: 4133
- 25b Schaefer BA, Margulieux GW, Small BL, Chirik PJ. Organometallics 2015; 34: 1307
- 26 Obligacion JV, Semproni SP, Pappas I, Chirik PJ. J Am Chem Soc 2016; 138: 10645
- 27 Lee B, Pabst TP, Hierlmeier G, Chirik PJ. Organometallics 2023; 42: 708
- 28 Ríos P, Borge J, Córdova FFD, Sciortino G, Lledós A, Rodríguez A. Chem Sci 2021; 12: 2540
- 29 Tendera L, Fantuzzi F, Marder TB, Radius U. Chem Sci 2023; 14: 2215
- 30a Ito H, Yamanaka H, Tateiwa J-I, Hosomi A. Tetrahedron Lett 2000; 41: 6821
- 30b Takahashi K, Ishiyama T, Miyaura N. Chem Lett 2000; 982
- 31 Zhang L, Hou Z. Chem Sci 2013; 4: 3395
- 32 Charman RSC, Hobson JA, Jackson RA, Mahon MF, Neale SE, Liptrot DJ. Chem Eur J 2024; 30: e202302704
- 33 Borner C, Kleeberg C. Eur J Inorg Chem 2014; 2014: 2486
- 34 Borner C, Tindall DJ, Kleeberg C. RSC Adv 2019; 9: 3900
- 35 Borner C, Anders L, Brandhorst K, Kleeberg C. Organometallics 2017; 36: 4687
- 36 Kleeberg C, Borner C. Organometallics 2018; 37: 4136
- 37 Drescher W, Kleeberg C. Inorg Chem 2019; 58: 8215
- 38a Lou X, Lin J, Kwok CY, Lyu H. Angew Chem Int Ed 2023; 62: e202312633
- 38b Liu Z, Lyu H. Eur J Org Chem 2025; 2500223
- 39a Scharnagl FK, Bose SK, Marder TB. Org Biomol Chem 2017; 15: 1738
- 39b Tung P, Schuhmacher A, Schilling PE, Bode JW, Mankad NP. Angew Chem 2022; 134: e202114513
- 39c Zhang X, Friedrich A, Marder TB. Chem Eur J 2022; 28: e202201329
- 40 Rickard CEF, Roper WR, Williamson A, Wright LJ. Organometallics 2000; 19: 4344
- 41 Drescher W, Kleeberg C. Dalton TransactionsDalton Trans 2022; 51: 4749
- 42 Câmpian MV, Harris JL, Jasim N, Perutz RN, Marder TB, Whitwood AC. Organometallics 2006; 25: 5093
- 43 Dai C, Stringer G, Marder TB. et al. Can J Chem 1996; 74: 2026
- 44 Lu N, Norman NC, Orpen AG, Quayle MJ, Timms PL, Whittell GRJ. Chem Soc, Dalton Trans 2000; 4032
- 45 Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J Am Chem Soc 2002; 124: 390
- 46 Nguyen P, Blom HP, Westcott SA, Taylor NJ, Marder TB. J Am Chem Soc 1993; 115: 9329
- 47 Wang G, Xu L, Li P. J Am Chem Soc 2015; 137: 8058
- 48 Iverson CN, Smith III MR. J Am Chem Soc 1995; 117: 4403
- 49 Lesley G, Nguyen P, Taylor NJ. et al. Organometallics 1996; 15: 5137
- 50 Ishiyama T, Matsuda N, Miyaura N, Suzuki A. J Am Chem Soc 1993; 115: 11018
- 51 Ishiyama T, Matsuda N, Murata M, Ozawa F, Suzuki A, Miyaura N. Organometallics 1996; 15: 713
- 52 Kerr A, Marder TB, Norman NC. et al. Chem Commun 1998; 319
- 53 Muessig JH, Prieschl D, Deißenberger A. et al. J Am Chem Soc 2018; 140: 13056
- 54a Norman N, áGuy Orpen A. J Chem Soc, Dalton Trans 1999; 1687
- 54b Westcott SA, Marder TB, Baker RT. et al. Polyhedron 2004; 23: 2665
- 55 Braunschweig H, Lutz M, Radacki K. Angew Chem Int Ed 2005; 44: 5647
- 56 Braunschweig H, Kupfer T, Lutz M, Radacki K, Seeler F, Sigritz R. Angew Chem Int Ed 2006; 45: 8048
- 57 Braunschweig H, Kaupp M, Adams CJ, Kupfer T, Radacki K, Schinzel S. J Am Chem Soc 2008; 130: 11376
- 58 Braunschweig H, Bertermann R, Brenner P. et al. Chem Eur J 2011; 17: 11828
- 59 Braunschweig H, Brenner P, Dewhurst RD. et al. Chem Eur J 2012; 18: 8605
- 60 Braunschweig H, Damme A. Chem Commun 2013; 49: 5216
- 61 Braunschweig H, Damme A, Kupfer T. Angew Chem Int Ed 2011; 50: 7179
- 62 Pospiech S, Bolte M, Lerner H-W, Wagner M. Organometallics 2014; 33: 6967
For selected reviews and books of applications of organoboron compounds in synthetic chemistry, biomedicine and material science, see:
For selected reviews and examples of metal boryl complexes, see:
For selected reviews and examples of TM-B(sp2) complexes in borylation reactions, see:
Wiebke Drescher (née Oschmann):