Abstract
As an alternative to the classical Grignard reaction, transition-metal catalyzed direct addition of aryl C-H bonds to carbonyl groups and their analogues have recently attracted increasing attention due to its atom economy, environmental benefits, abundance of C-H bonds as well as the scientific challenging to achieve mild C-H activations. This chapter briefly summarizes the recent progress in this field, categorized according to different metal catalysts. Applications to synthesize heterocycles and other useful molecules were highlighted as examples. Both the major challenges and the strategies to solve them are discussed in this chapter.
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References
Li C-J, Trost BM (2008) Green chemistry for chemical synthesis. Proc Natl Acad Sci 105:13197
Satoh T, Miura M (2010) Oxidative coupling of aromatic substrates with alkynes and alkenes under rhodium catalysis. Chem Eur J 16:11212
Song G, Wang F, Li X (2012) C–C, C–O and C–N bond formation via rhodium(III)-catalyzed oxidative C–H activation. Chem Soc Rev 41:3651
Patureau FW, Wencel-Delord J, Glorius F (2012) Cp*Rh-catalyzed C–H activations: versatile dehydrogenative cross-couplings of Csp2 C–H positions with olefins, alkynes, and arenes. Aldrichim Acta 45:31
Yang L, Huang H (2015) Transition-metal-catalyzed direct addition of unactivated C–H bonds to polar unsaturated bonds. Chem Rev 115:3468
Zhang X-S, Chen K, Shi Z-J (2014) Transition metal-catalyzed direct nucleophilic addition of C–H bonds to carbon–heteroatom double bonds. Chem Sci 5:2146
Colby DA, Tsai AS, Bergman RG, Ellman JA (2012) Rhodium catalyzed chelation-assisted C– H bond functionalization reactions. Acc Chem Res 45:814
Yan G, Wu X, Yang M (2013) Transition-metal-catalyzed additions of C–H bonds to C–X (X = N, O) multiple bonds via C–H bond activation. Org Biomol Chem 11:5558
Fukumoto Y, Sawada K, Hagihara M, Chatani N, Murai S (2002) [Ir4(CO)12]-catalyzed coupling reaction of imidazoles with aldehydes in the presence of a hydrosilane to give 2-substituted imidazoles. Angew Chem Int Ed 41:2779
Li B-J, Shi Z-J (2011) Ir-catalyzed highly selective addition of pyridyl C–H bonds to aldehydes promoted by triethylsilane. Chem Sci 2:488
Tsuchikama K, Hashimoto Y-k, Endo K, Shibata T (2009) Iridium-catalyzed selective synthesis of 4-substituted benzofurans and indoles via directed cyclodehydration. Adv Synth Catal 351:2850
Kuninobu Y, Nishina Y, Nakagawa C, Takai K (2006) Rhenium-catalyzed insertion of aldehyde into a C−H bond: synthesis of isobenzofuran derivatives. J Am Chem Soc 128:12376
Kuninobu Y, Nishina Y, Takai K (2007) Rhenium-catalyzed synthesis of naphthalene derivatives via insertion of aldehydes into a C–H bond. Tetrahedron 63:8463
Kuninobu Y, Tokunaga Y, Kawata A, Takai K (2006) Insertion of polar and nonpolar unsaturated molecules into carbon−rhenium bonds generated by C−H bond activation: synthesis of phthalimidine and indene derivatives. J Am Chem Soc 128:202
Geng X, Wang C (2015) Rhenium-Catalyzed [4 + 1] Annulation of Azobenzenes and Aldehydes via Isolable Cyclic Rhenium(I) Complexes. Org Lett 17:2434
Li Y, Zhang X-S, Li H, Wang W-H, Chen K, Li B-J, Shi Z-J (2012) Mechanistic understanding of Rh-catalyzed N-sulfonylaldimine insertion into aryl C–H bonds. Chem Sci 3:1634
Tauchert ME, Incarvito CD, Rheingold AL, Bergman RG, Ellman JA (2012) Mechanism of the rhodium(III)-catalyzed arylation of imines via C–H bond functionalization: inhibition by substrate. J Am Chem Soc 134:1482
Wang C (2013) Manganese-mediated C–C bond formation via C–H activation: from stoichiometry to catalysis. Synlett 24:1606
Kuninobu Y, Nishina Y, Takeuchi T, Takai K (2007) Manganese-catalyzed insertion of aldehydes into a C-H bond. Angew Chem Int Ed 46:6518
Ritleng V, Sirlin C, Pfeffer M (2002) Ru-, Rh-, and Pd-catalyzed C−C bond formation involving C−H activation and addition on unsaturated substrates: reactions and mechanistic aspects. Chem Rev 102:1731
Lim S-G, Ahn J-A, Jun C-H (2004) Ortho alkylation of aromatic ketimine with functionalized alkene by Rh(I) catalyst. Org Lett 6:4687
Ueura K, Satoh T, Miura M (2007) An efficient waste-free oxidative coupling via regioselective C−H bond cleavage: Rh/Cu-catalyzed reaction of benzoic acids with alkynes and acrylates under air. Org Lett 9:1407
Tsai AS, Tauchert ME, Bergman RG, Ellman JA (2011) Rhodium(III)-catalyzed arylation of Boc-Imines via C−H bond functionalization. J Am Chem Soc 133:1248
Li Y, Li B-J, Wang W-H, Huang W-P, Zhang X-S, Chen K, Shi Z-J (2011) Rhodium-catalyzed direct addition of aryl C–H bonds to N-Sulfonyl aldimines. Angew Chem Int Ed 50:2115
Yang L, Correia CA, Li C-J (2011) Grignard-type arylation of aldehydes via a rhodium-catalyzed C–H activation under mild conditions. Adv Synth Catal 353:1269
Hesp KD, Bergman RG, Ellman JA (2011) Expedient synthesis of N-acyl anthranilamides and β-enamine amides by the Rh(III)-catalyzed amidation of aryl and vinyl C–H bonds with isocyanates. J Am Chem Soc 133:11430
Hesp KD, Bergman RG, Ellman JA (2012) Rhodium-catalyzed synthesis of branched amines by direct addition of benzamides to imines. Org Lett 14:2304
Zhou B, Yang Y, Lin S, Li Y (2013) Rhodium-catalyzed direct addition of indoles to N-sulfonylaldimines. Adv Synth Catal 355:360
Wangweerawong A, Bergman RG, Ellman JA (2014) Asymmetric Synthesis of α-Branched Amines via Rh(III)-Catalyzed C–H Bond Functionalization. J Am Chem Soc 136:8520
Li Y, Zhang X-S, Chen K, He K-H, Pan F, Li B-J, Shi Z-J (2012) N-directing group assisted rhodium-catalyzed aryl C–H addition to aryl aldehydes. Org Lett 14:636
Zhang X-S, Zhu Q-L, Luo F-X, Chen G, Wang X, Shi Z-J (2013) Aromatic C–H addition to ketones: the effect of directing groups. Eur J Org Chem 2013:6530
Shi X, Li C-J (2012) A novel rhodium-catalyzed cascade cyclization: direct synthesis of 3-substituted phthalides from aldehydes and aromatic acids. Adv Synth Catal 354:2933
Lian Y, Bergman RG, Ellman JA (2012) Rhodium(III)-catalyzed synthesis of phthalides by cascade addition and cyclizationof benzimidates with aldehydes. Chem Sci 3:3088
Lian Y, Bergman RG, Lavis LD, Ellman JA (2013) Rhodium(III)-catalyzed indazole synthesis by C–H bond functionalization and cyclative capture. J Am Chem Soc 135:7122
Chen J, Chen P, Song C, Zhu J (2014) Rhodium(III)-catalyzed N-nitroso-directed C–H addition to ethyl 2-oxoacetate for cycloaddition/fragmentation synthesis of indazoles. Chem Eur J 20:14245
Gao K, Yoshikai N (2012) Cobalt-catalyzed arylation of aldimines via directed C–H bond functionalization: addition of 2-arylpyridines and self-coupling of aromatic aldimines. Chem Commun 48:4305
Yoshino T, Ikemoto H, Matsunaga S, Kanai M (2013) A cationic high-valent Cp*CoIII complex for the catalytic generation of nucleophilic organometallic species: directed C–H bond activation. Angew Chem Int Ed 52:2207
Yoshino T, Ikemoto H, Matsunaga S, Kanai M (2013) Cp*CoIII-catalyzed C2-selective addition of indoles to imines. Chem Eur J 19:9142
Hummel JR, Ellman JA (2015) Cobalt(III)-catalyzed synthesis of indazoles and furans by C–H bond functionalization/addition/cyclization cascades. J Am Chem Soc 137:490
Hummel JR, Ellman JA (2015) Cobalt(III)-catalyzed C–H bond amidation with isocyanates. Org Lett 17:2400
Acknowledgments
We are indebted to our colleagues, whose name are given in the list of references. We also thank the Canada Research Chair (Tier I) foundation; the CFI, NSERC, and FQRNT; and the CSC (China Scholarship Council) for a postdoctoral scholarship to Feng Wang.
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Wang, F., Liu, W., Li, CJ. (2016). Catalytic Grignard-Type Addition of Aryl C‐H Bonds to C=O and C=N Bonds. In: Tundo, P., He, LN., Lokteva, E., Mota, C. (eds) Chemistry Beyond Chlorine. Springer, Cham. https://doi.org/10.1007/978-3-319-30073-3_1
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