2.2 C—C Bond Formation by Alkyl C—H Activation

O. Baudoin

Abstract

In comparison to the wealth of methods recently developed for the catalytic functionalization of the C(sp²)—H bonds of arenes and hetarenes, relatively little work has focused on the functionalization of the unactivated C(sp³)—H bonds of alkyl fragments. This chapter highlights selected examples of the fast-growing literature on the catalytic functionalization of unactivated C(sp³)—H bonds through organometallic C—H activation, with an emphasis on the most synthetically useful methods. It covers heteroatom-directed C(sp³)—H activation with regard to cross coupling with alkenes, alkynes, and carbon monoxide, organoboron reagents, diaryliodonium salts, and organic halides. Also included is C(sp³)—H activation/intramolecular C—C coupling induced by oxidative addition and nondirected intermolecular C(sp³)—H arylation.

Schlüsselwörter

C(sp3)—H bond activation - carbon—carbon coupling - transition metals - palladium catalysis - ruthenium catalysis - alkylation

• 1 Dick AR, Sanford MS. Tetrahedron 2006; 62: 2439

• 2 Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010; 110: 704

• 3 Collet F, Dodd RH, Dauban P. Chem. Commun. 2009; 5061

• 4 Jazzar R, Hitce J, Renaudat A, Sofack-Kreutzer J, Baudoin O. Chem.–Eur. J. 2010; 16: 2654

• 5 Baudoin O. Chem. Soc. Rev. 2011; 40: 4902

• 6 Li H, Li B.-J, Shi Z.-J. Catal. Sci. Technol. 2011; 1: 191

• 7 Johansson CCC, Colacot TJ. Angew. Chem. Int. Ed. 2010; 49: 676

• 8 Yeung CS, Dong VM. Chem. Soc. Rev. 2011; 111: 1215

• 9 Jun C.-H, Hwang D.-C, Na S.-J. Chem. Commun. 1998; 1405

• 10 Kakiuchi F, Murai S. Acc. Chem. Res. 2002; 35: 826

• 11 Pan S, Endo K, Shibata T. Org. Lett. 2011; 13: 4692

• 12 Pan S, Matsuo Y, Endo K, Shibata T. Tetrahedron 2012; 68: 9009

• 13 Tsuchikama K, Kasagawa M, Endo K, Shibata T. Org. Lett. 2009; 11: 1821

• 14 Ishii Y, Chatani N, Kakiuchi F, Murai S. Organometallics 1997; 16: 3615

• 15 Chatani N, Asaumi T, Ikeda T, Yorimitsu S, Ishii Y, Kakiuchi F, Murai S. J. Am. Chem. Soc. 2000; 122: 12882

• 16 Chatani N, Asaumi T, Yorimitsu S, Ikeda T, Kakiuchi F, Murai S. J. Am. Chem. Soc. 2001; 123: 10935

• 17 Bergman SD, Storr TE, Prokopcová H, Aelvoet K, Diels G, Meerpoel L, Maes BUW. Chem.–Eur. J. 2012; 18: 10393

• 18 Hasegawa N, Charra V, Inoue S, Fukumoto Y, Chatani N. J. Am. Chem. Soc. 2011; 133: 8070

• 19 Yoo EJ, Wasa M, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 17378

• 20 Ackermann L. Chem. Rev. 2011; 111: 1315

• 21 Wasa M, Engle KM, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 3680

• 22 Stowers KJ, Fortner KC, Sanford MS. J. Am. Chem. Soc. 2011; 133: 6541

• 23 Pastine SJ, Gribkov DV, Sames D. J. Am. Chem. Soc. 2006; 128: 14220

• 24 Prokopcová H, Bergman SD, Aelvoet K, Smout V, Herrebout W, Van der Veken B, Meerpoel L, Maes BUW. Chem.–Eur. J. 2010; 16: 13063

• 25 Dastbaravardeh N, Schnürch M, Mihovilovic MD. Org. Lett. 2012; 14: 1930

• 26 Dastbaravardeh N, Kirchner K, Schnürch M, Mihovilovic MD. J. Org. Chem. 2013; 78: 658

• 27 Chen X, Goodhue CE, Yu J.-Q. J. Am. Chem. Soc. 2006; 128: 12634

• 28 Giri R, Maugel N, Li J.-J, Wang D.-H, Breazzano SP, Saunders LB, Yu J.-Q. J. Am. Chem. Soc. 2007; 129: 3510

• 29 Wang D.-H, Wasa M, Giri R, Yu J.-Q. J. Am. Chem. Soc. 2008; 130: 7190

• 30 Wasa M, Engle KM, Lin DW, Yoo EJ, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 19598

• 31 Kalyani D, Deprez NR, Desai LV, Sanford MS. J. Am. Chem. Soc. 2005; 127: 7330

• 32 Deprez NR, Sanford MS. J. Am. Chem. Soc. 2009; 131: 11234

• 33 Shabashov D, Daugulis O. Org. Lett. 2005; 7: 3657

• 34 Zaitsev VG, Shabashov D, Daugulis O. J. Am. Chem. Soc. 2005; 127: 13154

• 35 Shabashov D, Daugulis O. J. Am. Chem. Soc. 2010; 132: 3965

• 36 Reddy BVS, Reddy LR, Corey EJ. Org. Lett. 2006; 8: 3391

• 37 Tran LD, Daugulis O. Angew. Chem. Int. Ed. 2012; 51: 5188

• 38 Feng Y, Chen G. Angew. Chem. Int. Ed. 2010; 49: 958

• 39 He G, Chen G. Angew. Chem. Int. Ed. 2011; 50: 5192

• 40 Zhang S.-Y, He G, Nack WA, Zhao Y, Li Q, Chen G. J. Am. Chem. Soc. 2013; 135: 2124

• 41 Rodríguez N, Romero-Revilla JA, Fernández-Ibáñez MÁ, Carretero JC. Chem. Sci. 2013; 4: 175

• 42 Ano Y, Tobisu M, Chatani N. J. Am. Chem. Soc. 2011; 133: 12984

• 43 Gutekunst WR, Baran PS. J. Am. Chem. Soc. 2011; 133: 19076

• 44 Gutekunst WR, Gianatassio R, Baran PS. Angew. Chem. Int. Ed. 2012; 51: 7507

• 45 Wasa M, Engle KM, Yu J.-Q. J. Am. Chem. Soc. 2009; 131: 9886

• 46 Figg TM, Wasa M, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 14206

• 47 He J, Wasa M, Chan KSL, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 3387

• 48 Wasa M, Chan KSL, Zhang X.-G, He J, Miura M, Yu J.-Q. J. Am. Chem. Soc. 2012; 134: 18570

• 49 Campeau L.-C, Schipper DJ, Fagnou K. J. Am. Chem. Soc. 2008; 130: 3266

• 50 Schipper DJ, Campeau L.-C, Fagnou K. Tetrahedron 2009; 65: 3155

• 51 Mousseau JJ, Larivée A, Charette AB. Org. Lett. 2008; 10: 1641

• 52 Dyker G. Angew. Chem. Int. Ed. Engl. 1992; 31: 1023

• 53 Dyker G. J. Org. Chem. 1993; 58: 6426

• 54 Dyker G. Angew. Chem. Int. Ed. Engl. 1994; 33: 103

• 55 Dyker G. Chem. Ber. 1994; 127: 739

• 56 Catellani M, Ferioli L. Synthesis 1996; 769

• 57 Catellani M, Motti E, Ghelli S. Chem. Commun. 2000; 2003

• 58 Baudoin O, Herrbach A, Guéritte F. Angew. Chem. Int. Ed. 2003; 42: 5736

• 59 Chaumontet M, Piccardi R, Audic N, Hitce J, Peglion J.-L, Clot E, Baudoin O. J. Am. Chem. Soc. 2008; 130: 15157

• 60 Rousseaux S, Davi M, Sofack-Kreutzer J, Pierre C, Kefalidis CE, Clot E, Fagnou K, Baudoin O. J. Am. Chem. Soc. 2010; 132: 10706

• 61 Davi M, Comte A, Jazzar R, Baudoin O. Org. Synth. 2012; 89: 510

• 62 Kefalidis CE, Baudoin O, Clot E. Dalton Trans. 2010; 10528

• 63 Chaumontet M, Piccardi R, Baudoin O. Angew. Chem. Int. Ed. 2009; 48: 179

• 64 Ren H, Knochel P. Angew. Chem. Int. Ed. 2006; 45: 3462

• 65 Ren H, Li Z, Knochel P. Chem.–Asian J. 2007; 2: 416

• 66 Hitce J, Retailleau P, Baudoin O. Chem.–Eur. J. 2007; 13: 792

• 67 Lafrance M, Gorelsky SI, Fagnou K. J. Am. Chem. Soc. 2007; 129: 14570

• 68 Watanabe T, Oishi S, Fujii N, Ohno H. Org. Lett. 2008; 10: 1759

• 69 Rousseaux S, Gorelsky SI, Chung BKW, Fagnou K. J. Am. Chem. Soc. 2010; 132: 10692

• 70 Guyonnet M, Baudoin O. Org. Lett. 2012; 14: 398

• 71 Tsukano C, Okuno M, Takemoto Y. Angew. Chem. Int. Ed. 2012; 51: 2763

• 72 Sofack-Kreutzer J, Martin N, Renaudat A, Jazzar R, Baudoin O. Angew. Chem. Int. Ed. 2012; 51: 10399

• 73 Rousseaux S, Liégault B, Fagnou K. Chem. Sci. 2012; 3: 244

• 74 Ladd CL, Sustac Roman D, Charette AB. Org. Lett. 2013; 15: 1350

• 75 Saget T, Perez D, Cramer N. Org. Lett. 2013; 15: 1354

• 76 Giri R, Shi B.-F, Engle KM, Maugel N, Yu J.-Q. Chem. Soc. Rev. 2009; 38: 3242

• 77 Nakanishi M, Katayev D, Besnard C, Kündig EP. Angew. Chem. Int. Ed. 2011; 50: 7438

• 78 Larionov E, Nakanishi M, Katayev D, Besnard C, Kündig EP. Chem. Sci. 2013; 4: 1995

• 79 Anas S, Cordi A, Kagan HB. Chem. Commun. 2011; 47: 11483

• 80 Saget T, Lemouzy SJ, Cramer N. Angew. Chem. Int. Ed. 2012; 51: 2238

• 81 Katayev D, Nakanishi M, Bürgi T, Kündig EP. Chem. Sci. 2012; 3: 1422

• 82 Martin N, Pierre C, Davi M, Jazzar R, Baudoin O. Chem.–Eur. J. 2012; 18: 4480 Chem.–Eur. J. 2014; 20: 12341

• 83 Saget T, Cramer N. Angew. Chem. Int. Ed. 2012; 51: 12842

• 84 Dyker G, Heiermann J, Miura M, Inoh J.-I, Pivsa-Art S, Satoh T, Nomura M. Chem.–Eur. J. 2000; 6: 3426

• 85 Niwa T, Yorimitsu H, Oshima K. Org. Lett. 2007; 9: 2373

• 86 Bellomo A, Zhang J, Trongsiriwat N, Walsh PJ. Chem. Sci. 2013; 4: 849

• 87 Niwa T, Yorimitsu H, Oshima K. Org. Lett. 2008; 10: 4689

• 88 Burton PM, Morris JA. Org. Lett. 2010; 12: 5359

• 89 Song G, Su Y, Gong X, Han K, Li X. Org. Lett. 2011; 13: 1968