8.1.33.4 Transition-Metal-Catalyzed C—C Bond Formation with Organolithium Reagents (Update 2025)

Abstract

Organolithium compounds are among the most versatile and widely used reagents in organic synthesis. However, their high reactivity and basicity have historically limited their use as direct coupling partners in metal-catalyzed carbon—carbon bond forming methods. This review provides an update to the advances in this area, with a focus on highlighting reports during the period 2011–2023, that have revolutionized the field, propelling organolithium reagents to the forefront of strategies for constructing new C—C bonds using transition-metal catalysts.

Key words

organolithium compounds - C—C bond formation - cross-coupling reactions - allylic substitution - asymmetric catalysis - palladium catalysis - copper catalysis - iron catalysis - nickel catalysis - manganese catalysis

• 1 Pérez M, Fañanás-Mastral M, Bos PH, Rudolph A, Harutyunyan SR, Feringa BL. Nat. Chem. 2011; 3: 377

• 2 Hornillos V, Guduguntla S, Fañanás-Mastral M, Pérez M, Bos PH, Rudolph A, Harutyunyan SR, Feringa BL. Nat. Protoc. 2017; 12: 493

• 3 Huo L.-Q, Wang X.-H, Zhang Z, Jia Z, Peng X.-S, Wong HNC. Chem. Sci. 2023; 14: 1342

• 4 Manolikakes G. Science of Synthesis Knowledge Updates 2012; 1: 215

• 5 Falciola CA, Alexakis A. Eur. J. Org. Chem. 2008; 3765

• 6 Fañanás-Mastral M, Pérez M, Bos PH, Rudolph A, Harutyunyan SR, Feringa BL. Angew. Chem. Int. Ed. 2012; 51: 1922

• 7 Fañanás-Mastral M, Vitale R, Pérez M, Feringa BL. Chem.–Eur. J. 2015; 21: 4209

• 8 Pérez M, Fañanás-Mastral M, Hornillos V, Rudolph A, Bos PH, Harutyunyan SR, Feringa BL. Chem.–Eur. J. 2012; 18: 11880

• 9 Guduguntla S, Hornillos V, Tessier R, Fañanás-Mastral M, Feringa BL. Org. Lett. 2016; 18: 252

• 10 Guduguntla S, Gualtierotti J.-B, Goh SS, Feringa BL. ACS Catal. 2016; 6: 6591

• 11 Myers EL, Butts CP, Aggarwal VK. Chem. Commun. (Cambridge) 2006; 4434

• 12 Nájera C, Foubelo F, Sansano JM, Yus M. Tetrahedron 2022; 106–107: 132629

• 13 Science of Synthesis: Dynamic Kinetic Resolution (DKR) and Dynamic Kinetic Asymmetric Transformations (DYKAT). Bäckvall J.-E. Thieme; Stuttgart 2022.

• 14 Lautens M, Fagnou K, Hiebert S. Acc. Chem. Res. 2003; 36: 48

• 15 Lautens M, Gajda C, Chiu P. J. Chem. Soc., Chem. Commun. 1993; 1193

• 16 Bos PH, Rudolph A, Pérez M, Fañanás-Mastral M, Harutyunyan SR, Feringa BL. Chem. Commun. (Cambridge) 2012; 48: 1748

• 17 Xu K, Zheng Y, Ye Y, Liu D, Zhang W. Org. Lett. 2020; 22: 8836

• 18 Menard F, Perez D, Sustac Roman D, Chapman TM, Lautens M. J. Org. Chem. 2010; 75: 4056

• 19 Miura T, Takahashi Y, Murakami M. Chem. Commun. (Cambridge) 2007; 595

• 20 Piarulli U, Claverie C, Daubos P, Gennari C, Minnaard AJ, Feringa BL. Org. Lett. 2003; 5: 4493

• 21 Jacques R, Pullin RDC, Fletcher SP. Nat. Commun. 2019; 10: 21

• 22 Goh SS, Guduguntla S, Kikuchi T, Lutz M, Otten E, Fujita M, Feringa BL. J. Am. Chem. Soc. 2018; 140: 7052

• 23 Goh SS, Champagne PA, Guduguntla S, Kikuchi T, Fujita M, Houk KN, Feringa BL. J. Am. Chem. Soc. 2018; 140: 4986

• 24 Pizzolato SF, Giannerini M, Bos PH, Fañanás-Mastral M, Feringa BL. Chem. Commun. (Cambridge) 2015; 51: 8142

• 25 Vila C, Hornillos V, Fañanás-Mastral M, Feringa BL. Org. Biomol. Chem. 2014; 12: 9321

• 26 Murahashi S, Yamamura M, Yanagisawa K, Mita N, Kondo K. J. Org. Chem. 1979; 44: 2408

• 27 Giannerini M, Fañanás-Mastral M, Feringa BL. Nat. Chem. 2013; 5: 667

• 28 Vila C, Giannerini M, Hornillos V, Fañanás-Mastral M, Feringa BL. Chem. Sci. 2014; 5: 1361

• 29 Vila C, Cembellín S, Hornillos V, Giannerini M, Fañanás-Mastral M, Feringa BL. Chem.–Eur. J. 2015; 21: 15520

• 30 Heijnen D, Tosi F, Vila C, Stuart MCA, Elsinga PH, Szymanski W, Feringa BL. Angew. Chem. Int. Ed. 2017; 56: 3354

• 31 Chen P, Wang Z.-Y, Wang J.-X, Peng X.-S, Wong HNC. Org. Chem. Front. 2022; 9: 3438

• 32 Hornillos V, Giannerini M, Vila C, Fañanás-Mastral M, Feringa BL. Chem. Sci. 2015; 6: 1394

• 33 Ma S, Zhang A. J. Org. Chem. 1998; 63: 9601

• 34 Mateos-Gil J, Mondal A, Castiñeira Reis M, Feringa BL. Angew. Chem. Int. Ed. 2020; 59: 7823

• 35 Helbert H, Visser P, Hermens JGH, Buter J, Feringa BL. Nat. Catal. 2020; 3: 664

• 36 Mondal A, Visser P, Doze AM, Buter J, Feringa BL. Chem. Commun. (Cambridge) 2021; 57: 7529

• 37 Hornillos V, Giannerini M, Vila C, Fañanás-Mastral M, Feringa BL. Org. Lett. 2013; 15: 5114

• 38 Heijnen D, Hornillos V, Corbet BP, Giannerini M, Feringa BL. Org. Lett. 2015; 17: 2262

• 39 Scherpf T, Steinert H, Großjohann A, Dilchert K, Tappen J, Rodstein I, Gessner VH. Angew. Chem. Int. Ed. 2020; 59: 20596

• 40 Yang Z.-K, Wang D.-Y, Minami H, Ogawa H, Ozaki T, Saito T, Miyamoto K, Wang C, Uchiyama M. Chem.–Eur. J. 2016; 22: 15693

• 41 Dilauro G, Quivelli AF, Vitale P, Capriati V, Perna FM. Angew. Chem. Int. Ed. 2019; 58: 1799

• 42 Vila C, Hornillos V, Giannerini M, Fañanás-Mastral M, Feringa BL. Chem.–Eur. J. 2014; 20: 13078

• 43 O’Brien CJ, Kantchev EAB, Valente C, Hadei N, Chass GA, Lough A, Hopkinson AC, Organ MG. Chem.–Eur. J. 2006; 12: 4743

• 44 Chartoire A, Lesieur M, Falivene L, Slawin AMZ, Cavallo L, Cazin CSJ, Nolan SP. Chem.–Eur. J. 2012; 18: 4517

• 45 Çalimsiz S, Sayah M, Mallik D, Organ MG. Angew. Chem. Int. Ed. 2010; 49: 2014

• 46 Giannerini M, Hornillos V, Vila C, Fañanás-Mastral M, Feringa BL. Angew. Chem. Int. Ed. 2013; 52: 13329

• 47 Kleijn RH, Meijer J, Oostveen EA, Vermeer P. J. Organomet. Chem. 1982; 224: 399

• 48 Zhao J, Liu Y, He Q, Li Y, Ma S. Chem.–Eur. J. 2009; 15: 11361

• 49 Ma S, He Q. Angew. Chem. Int. Ed. 2004; 43: 988

• 50 Chinchilla R, Nájera C. Chem. Soc. Rev. 2011; 40: 5084

• 51 Griesbeck AG, Soldevilla A. Science of Synthesis 2008; 43: 359

• 52 Riant O, Rout SK. Science of Synthesis: Dual Catalysis in Organic Synthesis 2019; 1: 9

• 53 Noyori S, Nishihara Y, In: Applied Cross-Coupling Reactions Nishihara Y. Springer Berlin 2013; 177–202

• 54 Castelló LM, Hornillos V, Vila C, Giannerini M, Fañanás-Mastral M, Feringa BL. Org. Lett. 2015; 17: 62

• 55 Scherpf T, Schwarz C, Scharf LT, Zur J.-A, Helbig A, Gessner VH. Angew. Chem. Int. Ed. 2018; 57: 12859

• 56 Wenkert E, Han A.-L, Jenny C.-J. J. Chem. Soc., Chem. Commun. 1988; 975

• 57 Reeves JT, Fandrick DR, Tan Z, Song JJ, Lee H, Yee NK, Senanayake CH. Org. Lett. 2010; 12: 4388

• 58 Blakey SB, MacMillan DWC. J. Am. Chem. Soc. 2003; 125: 6046

• 59 Xie L.-G, Wang Z.-X. Angew. Chem. Int. Ed. 2011; 50: 4901

• 60 Slavík P, Trowse BR, O’Brien P, Smith DK. Nat. Chem. 2023; 15: 319

• 61 Visser P, Feringa BL. Chem. Commun. (Cambridge) 2023; 59: 5539

• 62 García-Álvarez J, Hevia E, Capriati V. Chem.–Eur. J. 2018; 24: 14854

• 63 Antenucci A, Dughera S. ChemistrySelect 2023; 8 e202303046

• 64 Fuji K, Tamba S, Shono K, Sugie A, Mori A. J. Am. Chem. Soc. 2013; 135: 12208

• 65 Heijnen D, Gualtierotti J.-B, Hornillos V, Feringa BL. Chem.–Eur. J. 2016; 22: 3991

• 66 Leiendecker M, Hsiao C.-C, Guo L, Alandini N, Rueping M. Angew. Chem. Int. Ed. 2014; 53: 12912

• 67 Guo L, Leiendecker M, Hsiao C.-C, Baumann C, Rueping M. Chem. Commun. (Cambridge) 2015; 51: 1937

• 68 Nolla-Saltiel R, Bedford RB. Science of Synthesis: Base-Metal Catalysis 2022; 2: 371

• 69 Jia Z, Liu Q, Peng X.-S, Wong HNC. Nat. Commun. 2016; 7: 10614

• 70 Cahiez G, Habiak V, Duplais C, Moyeux A. Angew. Chem. Int. Ed. 2007; 46: 4364

• 71 Lu X.-L, Shannon M, Peng X.-S, Wong HNC. Org. Lett. 2019; 21: 2546

• 72 Chen P, Wang Z.-Y, Peng X.-S, Wong HNC. Org. Lett. 2021; 23: 4385

• 73 Liu Q, Wang Z.-Y, Peng X.-S, Wong HNC. J. Org. Chem. 2018; 83: 6325

• 74 Nagano T, Hayashi T. Org. Lett. 2005; 7: 491

• 75 Cahiez G, Chaboche C, Mahuteau-Betzer F, Ahr M. Org. Lett. 2005; 7: 1943

• 76 Xu X, Cheng D, Pei W. J. Org. Chem. 2006; 71: 6637

• 77 Surry DS, Fox DJ, Macdonald SJF, Spring DR. Chem. Commun. (Cambridge) 2005; 2589

• 78 Toummini D, Ouazzani F, Taillefer M. Org. Lett. 2013; 15: 4690

• 79 Wang Z.-Y, Peng X.-S, Wong HNC. Asian J. Org. Chem. 2020; 9: 1834

• 80 Zhong Z, Wang Z.-Y, Ni S.-F, Dang L, Lee HK, Peng X.-S, Wong HNC. Org. Lett. 2019; 21: 700

• 81 Liu Y, Bergès J, Zaid Y, Chahdi FO, Van Der Lee A, Harakat D, Clot E, Jaroschik F, Taillefer M. J. Org. Chem. 2019; 84: 4413