2.8 Iron-Catalyzed C—H Functionalization

S. Banerjee;   L. Ilies 

Abstract

The direct functionalization of an organic substrate via transition-metal-catalyzed C—H bond activation is a powerful tool for building molecular complexity. Despite the abundance, low cost, and low toxicity of iron, which make it an ideal metal for sustainable catalysis, iron-catalyzed C—H activation has been less investigated compared with catalysis based on precious metals such as palladium or iridium. In this chapter, selected examples of iron-catalyzed activation of a C—H bond to create a new C—C bond are described. Arylation, hetarylation, alkenylation, and alkylation of C(sp²)—H and C(sp³)—H bonds is discussed. Most of the substrates require a directing group, but several examples of non-directed reactions are also presented. The functionalization of a C—H bond has been achieved by using organometallic reagents, organic halides and pseudohalides, multiple bonds such as alkenes and alkynes, and arenes or hetarenes as the reaction partner.

Schlüsselwörter

C—H activation - C—H functionalization - C—C bond formation - iron catalysis - arylation - alkenylation - alkylation - directing group - bipyridine ligands - phosphine ligands - NHC ligands - organometallic reagents - alkyl halides - alkenes - alkynes - arenes - hetarenes

• 1 Handbook of C-H Transformations. Dyker G. Wiley-VCH; Weinheim, Germany 2005

• 2 C-H Bond Activation and Catalytic Functionalization. Dixneuf PH, Doucet H. Springer; Berlin 2016. Topics in Organometallic Chemistry

• 3 Nakamura E, Sato K. Nat. Mater. 2011; 10: 158

• 4 Iron Catalysis in Organic Chemistry: Reactions and Applications. Plietker B. Wiley-VCH; Weinheim, Germany 2008

• 5 The Chemistry of Organoiron Compounds. Marek I, Rappoport Z. Wiley; Chichester, U. K. 2014

• 6 Sun C.-L, Li B.-J, Shi Z.-J. Chem. Rev. 2011; 111: 1293

• 7 Cera G, Ackermann L. Top. Curr. Chem. 2016; 374: 191

• 8 Shang R, Ilies L, Nakamura E. Chem. Rev. 2017; 117: 9086

• 9 Yoshikai N. Isr. J. Chem. 2017; 57: 1117

• 10 Ilies L. Bull. Chem. Soc. Jpn. 2021; 94: 404

• 11 Fürstner A, Leitner A, Méndez M, Krause H. J. Am. Chem. Soc. 2002; 124: 13856

• 12 Sherry BD, Fürstner A. Acc. Chem. Res. 2008; 41: 1500

• 13 Boddie TE, Carpenter SH, Baker TM, DeMuth JC, Cera G, Brennessel WW, Ackermann L, Neidig ML. J. Am. Chem. Soc. 2019; 141: 12338

• 14 Bhatia S, DeMuth JC, Neidig ML. Chem. Commun. (Cambridge) 2021; 57: 12784

• 15 Sun Y, Tang H, Chen K, Hu L, Yao J, Shaik S, Chen H. J. Am. Chem. Soc. 2016; 138: 3715

• 16 Bagga MM, Pauson PL, Preston FJ, Reed RI. Chem. Commun. 1965; 543

• 17 Tolman CA, Ittel SD, English AD, Jesson JP. J. Am. Chem. Soc. 1978; 100: 4080

• 18 Jones WD, Foster GP, Putinas JM. J. Am. Chem. Soc. 1987; 109: 5047

• 19 Norinder J, Matsumoto A, Yoshikai N, Nakamura E. J. Am. Chem. Soc. 2008; 130: 5858

• 20 Yoshikai N, Matsumoto A, Norinder J, Nakamura E. Angew. Chem. Int. Ed. 2009; 48: 2925

• 21 Gu Q, Al Mamari HH, Graczyk K, Diers E, Ackermann L. Angew. Chem. Int. Ed. 2014; 53: 3868

• 22 Schmiel D, Butenschön H. Organometallics 2017; 36: 4979

• 23 Shang R, Ilies L, Asako S, Nakamura E. J. Am. Chem. Soc. 2014; 136: 14349

• 24 Ilies L, Itabashi Y, Shang R, Nakamura E. ACS Catal. 2017; 7: 89

• 25 Ilies L, Kobayashi M, Matsumoto A, Yoshikai N, Nakamura E. Adv. Synth. Catal. 2012; 354: 593

• 26 Doba T, Matsubara T, Ilies L, Shang R, Nakamura E. Nat. Catal. 2019; 2: 400

• 27 Doba T, Ilies L, Sato W, Shang R, Nakamura E. Nat. Catal. 2021; 4: 631

• 28 Wong MY, Yamakawa T, Yoshikai N. Org. Lett. 2015; 17: 442

• 29 Jia T, Zhao C, He R, Chen H, Wang C. Angew. Chem. Int. Ed. 2016; 55: 5268

• 30 Mo J, Messinis AM, Oliveira JCA, Demeshko S, Meyer F, Ackermann L. ACS Catal. 2021; 11: 1053

• 31 Shang R, Ilies L, Nakamura E. J. Am. Chem. Soc. 2016; 138: 10132

• 32 Asako S, Ilies L, Nakamura E. J. Am. Chem. Soc. 2013; 135: 17755

• 33 Ilies L, Matsubara T, Ichikawa S, Asako S, Nakamura E. J. Am. Chem. Soc. 2014; 136: 13126

• 34 Fruchey ER, Monks BM, Cook SP. J. Am. Chem. Soc. 2014; 136: 13130

• 35 Monks BM, Fruchey ER, Cook SP. Angew. Chem. Int. Ed. 2014; 53: 11065

• 36 Cera G, Haven T, Ackermann L. Angew. Chem. Int. Ed. 2016; 55: 1484

• 37 Loup J, Zell D, Oliveira JCA, Keil H, Stalke D, Ackermann L. Angew. Chem. Int. Ed. 2017; 56: 14197

• 38 Ilies L, Zhou Y, Yang H, Matsubara T, Shang R, Nakamura E. ACS Catal. 2018; 8: 11478

• 39 Kimura N, Kochi T, Kakiuchi F. J. Am. Chem. Soc. 2017; 139: 14849

• 40 Kimura N, Kochi T, Kakiuchi F. Asian J. Org. Chem. 2019; 8: 1115

• 41 Kimura N, Katta S, Kitazawa Y, Kochi T, Kakiuchi F. J. Am. Chem. Soc. 2021; 143: 4543

• 42 Messinis AM, Finger LH, Hu L, Ackermann L. J. Am. Chem. Soc. 2020; 142: 13102

• 43 Shang R, Ilies L, Matsumoto A, Nakamura E. J. Am. Chem. Soc. 2013; 135: 6030

• 44 Sekine M, Ilies L, Nakamura E. Org. Lett. 2013; 15: 714

• 45 Matsumoto A, Ilies L, Nakamura E. J. Am. Chem. Soc. 2011; 133: 6557

• 46 Matsuoka W, Ito H, Sarlah D, Itami K. Nat. Commun. 2021; 12: 3940

• 47 Ilies L, Matsumoto A, Kobayashi M, Yoshikai N, Nakamura E. Synlett 2012; 23: 2381

• 48 Adak L, Yoshikai N. Tetrahedron 2012; 68: 5167