Abstract
Over the years, transition metal catalyzed reactions, such as C–H activation reaction, have brought in a paradigm shift in the practice of organic synthesis. Many complex targets could be synthesized using C–H activation strategies. In pursuit of improving the performance of catalytic reactions, various additives have generally been used as a key strategy. Additives, such as Lewis acids, Brønsted acids and metal salts, were found to have a dramatic influence in improving the yield and/or selectivities of various catalytic transformations. Although the impact additives have been widely acknowledged, the molecular basis towards understanding the origin of how these additives impact the energetics of catalytic reactions have remained rather scattered all over literature. In this review, we compile a large number of important examples where molecular understanding of the role of additives was established by using modern computational chemistry tools. Notably different energetics, proposals on the likely involvement of newer intermediates, nature of the turn-over limiting step and access to lower energy pathway all could be identified by explicit inclusion of additives in the mechanistic models. We believe that explicit consideration of additives is important toward identifying a more reasonable reaction mechanism of catalytic reactions.
Similar content being viewed by others
References
Rogge T, Kaplaneris N, Chatani N, Kim J, Chang S, Punji B, Schafer LL, Musaev DJ, Delord JW, Roberts CA, Sarpong RS, Wilson ZE, Brimble MA, Johansson MJ, Ackermann L (2021) Nat Rev Methods Primers 1:43
Kim DS, Park WJ, Jun CH (2017) Chem Rev 117:8977–9015
Dalton T, Faber T, Glorius F (2021) ACS Cent Sci 7:245–261
Cheng G-J, Zhang X, Chung LW, Xu L, Wu Y-D (2015) J Am Chem Soc 137:1706–1725
Zhang X, Chung LW, Wu Y-D (2016) Acc Chem Res 49:1302–1310
Shilov AE (1997) Shul’pin, G. B. Chem Rev 97:2879–2932
Vastine BA, Hall MB (2009) Coord Chem Rev 253:1202–1218
Ess DH, Goddard WA III, Periana RA (2010) Organometallics 29:6459–6472
Balcells D, Clot E, Eisenstein O (2010) Chem Rev 110:749–823
Funes-Ardoiz I, Maseras F (2018) ACS Catal 8:1161–1172
Lapointe D, Fagnou K (2010) Chem Lett 39:1118–1126
Gorelsky SI, Lapointe D, Fagnou K (2008) J Am Chem Soc 130:10848–10849
Lafrance M, Fagnou K (2006) J Am Chem Soc 128:16496–16497
Neufeldt SR, Sanford MS (2012) Acc Chem Res 45:936–946
Shulpin GB (2010) Org Biomol Chem 8:4217–4228
Sciortino G, Maseras F (2021). Top Catal. https://doi.org/10.1007/s11244-021-01493-2
Davies DL, Donald SMA, Macgregor SA (2005) J Am Chem Soc 127:13754–13755
Albrecht M (2010) Chem Rev 110:576–623
Ito J-I, Kaneda T, Nishiyama H (2014) Organometallics 33:6413–6419
Fujihara T, Yoshida A, Satou M, Tanji Y, Terao J, Tsuji Y (2016) Catal Commun 84:71–74
Boutadla Y, Davies DL, Macgregor SA, Poblador-Bahamonde AI (2009) Dalton Trans 30:5820–5831
Cornaton Y, Djukic J-P (2019) Phys Chem Chem Phys 21:20486–20498
Nielson AJ, Harrison JA, Sajjad MA, Schwerdtfeger P (2020) Eur J Inorg Chem 27:2639–2650
Sajjad MA, Schwerdtfeger P, Harrison JA, Nielson AJ (2020) Eur J Inorg Chem 2020:2603–2614
Harrison JH, Nielson AJM, Sajjad A, Schwerdtfeger P (2019) Organometallics 38:1903–1916
Nedd S, Alexandrova AN (2015) Phys Chem Chem Phys 17:1347–1353
Sanhueza IA, Wagner AM, Sanford MS, Schoenebeck F (2013) Chem Sci 4:2767–2775
Wang X-C, Hu Y, Bonacorsi S, Hong Y, Burrell R, Yu J-Q (2013) J Am Chem Soc 135:10326–10329
Haines BE, Yu J-Q, Musaev DG (2018) Chem Sci 9:1144–1154
Liu J-B, Tian Y-Y, Zhang X, Wang L-L, Chen D-Z (2018) Dalton Trans 47:4893–4901
Wasa M, Engle KM, Yu J-Q (2009) J Am Chem Soc 131:9886–9887
Figg TM, Wasa M, Yu J-Q, Musaev DG (2013) J Am Chem Soc 135:14206–14214
Schwarzer MC, Konno R, Hojo T, Ohtsuki A, Nakamura K, Yasutome A, Takahashi H, Shimasaki T, Tobisu M, Chatani N, Mori S (2017) J Am Chem Soc 139:10347–10358
Li B-W, Wang M-Y, Fang S, Liu J-Y (2019) Organometallics 38:2189–2198
Xu L-P, Haines BE, Ajitha MJ, Murakami K, Itami K, Musaev DG (2020) ACS Catal 10:3059–3073
Dewyer AL, Zimmerman PM (2017) ACS Catal 7:5466–5477
Ling B, Liu Y, Jiang Y-Y, Liu P, Bi S (2019) Organometallics 38:1877–1886
Song X, Doan BND, Zhang X, Lee R, Fan X (2020) Org Lett 22:46–51
Lv K, Jiang Y, Han L, Liu T, Bi S (2019) Mol Catal 462:77–84
Mohr Y, Renom-Carrasco M, Demarcy C, Quadrelli EA, Camp C, Wisser FM, Clot E, Thieuleux C, Canivet J (2020) ACS Catal 10:2713–2719
Zhang Q, Yu H-Z, Fu Y (2013) Organometallics 32:4165–4173
Simonetti M, Kuniyil R, Macgregor SA, Larrosa I (2018) J Am Chem Soc 140:11836–11847
Kim Y, Park Y, Chang S (2018) ACS Cent Sci 4:768–775
Muto K, Yamaguchi J, Itami K (2012) J Am Chem Soc 134:169–172
Xu H, Muto K, Yamaguch J, Zhao C, Itami K, Musaev DG (2014) J Am Chem Soc 136:14834–14844
Kim JH, Greβies S, Glorius F (2016) Angew Chem Int Ed 55:5577–5581
Wang Q, Huang F, Jiang L, Zhang C, Sun C, Liu J, Chen D (2018) Inorg Chem 57:2804–2814
Chan KW, Lam E, D’Anna V, Allouche F, Michel C, Safonova OV, Sautet P, Copéret C (2018) J Am Chem Soc 140:11395–11401
Chan JZ, Yesilcimen A, Cao M, Zhang Y, Zhang B, Wasa M (2020) J Am Chem Soc 142:16493–16505
Tischlera O, Kovácsa S, Érseka G, Králla P, Darub J, Stirling A, Nováka Z (2017) J Mol Catal A 426:444–450
Nakao Y, Morita E, Idei H, Hiyama T (2011) J Am Chem Soc 133:3264–3267
Anand M, Sunoj RB (2012) Org Lett 14:4584–4587
Yang L, Semba K, Nakao Y (2017) Angew Chem Int Ed 56:4853–4857
Singh V, Nakao Y, Sakaki S, Deshmukh MM (2017) J Org Chem 82:289–301
Gao XA, Yan RU, Wang XX, Yan H, Li J, Guo H, Huang GS (2012) J Org Chem 77:7700–7705
Athira C, Sunoj RB (2017) Org Biomol Chem 15:246–255
Theveau L, Verrier C, Lassalas P, Martin T, Dupas G, Querolle O, Hijfte LV, Marsais F, Hoarau C (2011) Chem Eur J 17:14450–14463
Wang H, Liu C, Zhang D (2018) J Organomet Chem 854:15–26
Zhang B-S, Li Y, An Y, Zhang Z, Liu C, Wang X-G, Liang Y-M (2018) ACS Catal 8:11827–11833
Vana J, Bartacek J, Hanusek J, Roithova J, Sedlak M (2019) J Org Chem 84:12746–12754
Li JF, Zhao RF, She MY, Zhang J, Yin B, Zhang SY, Li JL (2019) Org Chem Front 6:2607–2618
Yuan B, Guo X, Wang G, Huang H, Zhang F, Xu J, He R (2019) New J Chem 43:4291–4305
Deb A, Hazra A, Peng Q, Paton RS, Maiti D (2017) J Am Chem Soc 139:763–775
Wang Q, Chen R, Lou J, Zhang DH, Zhou Y-G, Yu Z (2019) ACS Catal 9:11669–11675
Aihara Y, Chatani N (2014) J Am Chem Soc 136:898–901
Singh SKS, Sunoj RB (2017) J Org Chem 82:9619–9626
Yoo EJ, Ma S, Mei T-S, Chan KSL, Yu J-Q (2011) J Am Chem Soc 133:7652–7655
Leow D, Li G, Mei T-S, Yu J-Q (2012) Nature 486:518–522
Fang L, Saint-Denis TG, Taylor BLH, Ahlquist S, Hong K, Liu S, Han L, Houk KN, Yu J-Q (2017) J Am Chem Soc 139:10702–10714
Mudarra ÁL, Salinas SM, Pérez-Temprano MH (2019) Org Biomol Chem 17:1655–1667
Powers DC, Ritter T (2013) Organometallics 32(7):2042–2045
Pérez-Temprano MH, Casares JA, Espinet P (2012) Chem Eur J 18:1864–1884
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 (2014) J Am Chem Soc 136:344–355
Anand M, Sunoj RB, Schaefer HF (2014) J Am Chem Soc 136:5535–5538
Murahashi T, Kurosawa H (2002) Coord Chem Rev 231:207–228
Petretto GL, Rourke JP, Maidich L, Stoccoro S, Cinellu MA, Minghetti G, Clarkson GJ, Zucca A (2012) Organometallics 31:2971–2977
Bhattacharya T, Dutta S, Maiti D (2021) ACS Catal 11:9702–9714
Yoo EJ, Ma S, Mei T-S, Chan KSL, Yu J-Q (2016) ACS Catal 6:696–708
Anand M, Sunoj RB, Schaefer HF (2016) ACS Catal 6:696–708
Feng W, Wang T, Liu D, Wang X, Dang Y (2019) ACS Catal 9:6672–6680
Bhaskararao B, Singh S, Anand M, Verma P, Prakash P, Athira C, Malakar S, Schaefer HF, Sunoj RB (2020) Chem Sci 11:208–216
Feng C-G, Ye M, Xiao K-J, Li S, Yu J-Q (2013) J Am Chem Soc 135:9322–9325
Wang G-W, Yuan T-T, Li D-D (2011) Angew Chem Int Ed 50:1380–1383
Tobisu M, Ano Y, Chatani N (2009) Org Lett 11:3250–3252
Wang L, Huang J, Peng S, Liu H, Jiang X, Wang J (2013) Angew Chem Int Ed 52:1768–1772
Kozuch S, Shaik S (2011) Acc Chem Res 44:101–110
Chen Y-Q, Singh S, Wu Y, Wang Z, Hao W, Verma P, Qiao JX, Sunoj RB, Yu J-Q (2020) J Am Chem Soc 142:9966–9974
Phipps RJ, Gaunt MJ (2009) Science 323:1593–1597
Fu J, Huo X, Lia B, Zhang W (2017) Org Biomol Chem 15:9747–9759
Wu Y, Huo X (2020) Zhang. Chem Eur J 26:4895–4916
Jiang Y-Y, Zhang Q, Yu H, Fu Y (2015) ACS Catal 5:1414–1423
Musaev DG, Liebeskind LS (2009) Organometallics 28:4639–4642
Kumar P, Kapur M (2019) Org Lett 21:2134–2138
Zhang J, Han L, Bi S, Liu T (2020) J Org Chem 85:8387–8396
Musgrave CB III, Zhu W, Coutard N, Ellena JF, Dickie DA, Gunnoe TB, Goddard WA III (2021) ACS Catal 11:5688–5702
Jones AW, Rank CK, Becker Y, Malchau C, Funes-Ardoiz I, Maseras F, Patureau FW (2018) Chem Eur J 24:15178–15184
Funes-Ardoiz I, Maseras F (2016) Angew Chem Int Ed 55:2764–2767
Racowski JM, Ball ND, Sanford MS (2011) J Am Chem Soc 133:18022–18025
Maleckis A, Kampf JW, Sanford MS (2013) J Am Chem Soc 135:6618–6625
Xing YM, Zhang L, Fang DC (2015) Organometallics 34:770–777
Zhang LL, Zhang L, Li SJ, Fang DC (2018) Dalton Trans 47:6102–6111
Osberger TJ, White MC (2014) J Am Chem Soc 136:11176–11181
Sreedhar DB, Sunoj RB (2019) Org Biomol Chem 17:7723–7734
Jindal G, Sunoj RB (2014) J Am Chem Soc 136(45):15998–16008
Chai Z, Rainey TJ (2012) J Am Chem Soc 134:3615–3618
Wang X-G, Li Y, Liu H-C, Zhang B-S, Gou X-Y, Wang Q, Ma J-M, Liang Y-M (2019) J Am Chem Soc 141:13914–13922
Omer HM, Liu P (2019) ACS Omega 4:5209–5220
Zhou D-G, Wang P (2020) New J Chem 44:2833–2846
Shibata M, Ito H, Itami K (2018) J Am Chem Soc 140:2196–2205
Li H, Ma X, Zhang B, Lei M (2016) Organometallics 35:3301–3310
Yin G, Kalvet I, Englert U, Schoenebeck F (2015) J Am Chem Soc 137:4164–4172
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Ghosh, S., Shilpa, S., Athira, C. et al. Role of Additives in Transition Metal Catalyzed C–H Bond Activation Reactions: A Computational Perspective. Top Catal 65, 141–164 (2022). https://doi.org/10.1007/s11244-021-01527-9
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11244-021-01527-9