Selective sp 3 C-H alkylation via polarity-match-based cross-coupling

Nature

Volumn 547, Issue 7661, 2017, Pages 79-83

  Le, Chip ^a   Liang, Yufan ^a   Evans, Ryan W ^a   Li, Ximing ^a   MacMillan, David W C ^a  

^a PRINCETON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUP; AMINE; CARBON; ETHER DERIVATIVE; HALIDE; HYDROGEN; NICKEL; SULFIDE;

CARBON; CATALYSIS; CHEMICAL BINDING; CHEMICAL REACTION; CHEMISTRY; HYDROGEN; MOLECULAR ANALYSIS; NICKEL; ORGANIC COMPOUND; REDOX CONDITIONS;

ALKYLATION; ARTICLE; ARYLATION; ATOM; CATALYSIS; CATALYST; CONTROLLED STUDY; COVALENT BOND; CROSS COUPLING REACTION; ELECTRON TRANSPORT; PRIORITY JOURNAL; CHEMISTRY; HYDROGEN BOND; OXIDATION REDUCTION REACTION; PROCEDURES; RADIATION RESPONSE; SYNTHESIS;

ALKYLATION; CARBON; CATALYSIS; CHEMISTRY TECHNIQUES, SYNTHETIC; HYDROGEN; HYDROGEN BONDING; NICKEL; OXIDATION-REDUCTION;

EID: 85022215653     PISSN: 00280836     EISSN: 14764687     Source Type: Journal    
DOI: 10.1038/nature22813     Document Type: Article

References (30)

1. Davies, H. M. L. & Morton, D. Recent advances in C-H functionalization. J. Org. Chem. 81, 343-350 (2016).
2. Chen, X., Engle, K. M., Wang, D.-H. & Yu, J.-Q. Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality. Angew. Chem. Int. Ed. 48, 5094-5115 (2009).
3. Ackermann, L. Metal-catalyzed direct alkylations of (hetero)arenes via C-H bond cleavages with unactivated alkyl halides. Chem. Commun. 46, 4866-4877 (2010).
4. Lyons, T. W. & Sanford, M. S. Palladium-catalyzed ligand-directed C H functionalization reactions. Chem. Rev. 110, 1147-1169 (2010).
5. Colby, D. A., Tsai, A. S., Bergman, R. G. & Ellman, J. A. Rhodium catalyzed chelation-assisted C-H bond functionalization reactions. Acc. Chem. Res. 45, 814-825 (2012).
6. Schönherr, H. & Cernak, T. Profound methyl effects in drug discovery and a call for new C-H methylation reactions. Angew. Chem. Int. Ed. 52, 12256-12267 (2013).
7. Zhang, Y.-H., Shi, B.-F. & Yu, J.-Q. Palladium(II)-catalyzed ortho alkylation of benzoic acids with alkyl halides. Angew. Chem. Int. Ed. 48, 6097-6100 (2009).
8. Aihara, Y. & Chatani, N. Nickel-catalyzed direct alkylation of C-H bonds in benzamides and acrylamides with functionalized alkyl halides via bidentatechelation assistance. J. Am. Chem. Soc. 135, 5308-5311 (2013).
9. Ackermann, L., Novák, P., Vicente, R. & Hofmann, N. Ruthenium-catalyzed regioselective direct alkylation of arenes with unactivated alkyl halides through C-H bond cleavage. Angew. Chem. Int. Ed. 48, 6045-6048 (2009).
10. Ilies, L., Matsubara, T., Ichikawa, S., Asako, S. & Nakamura, E. Iron-catalyzed directed alkylation of aromatic and olefinic carboxamides with primary and secondary alkyl tosylates, mesylates, and halides. J. Am. Chem. Soc. 136, 13126-13129 (2014).
11. Shabashov, D. & Daugulis, O. Auxiliary-assisted palladium-catalyzed arylation and alkylation of sp2 and sp3 carbon hydrogen bonds. J. Am. Chem. Soc. 132, 3965-3972 (2010).
12. Zhang, S.-Y., Li, Q., He, G., Nack, W. A. & Chen, G. Stereoselective synthesis of-alkylated-amino acids via palladium-catalyzed alkylation of unactivated methylene C(sp3)-H bonds with primary alkyl halides. J. Am. Chem. Soc. 135, 12135-12141 (2013).
13. Zhu, R.-Y., He, J., Wang, X.-C. & Yu, J.-Q. Ligand-promoted alkylation of C(sp3)-H and C(sp2)-H bonds. J. Am. Chem. Soc. 136, 13194-13197 (2014).
14. Adams, J. et al. Rhodium acetate catalyzes the addition of carbenoids-to ether oxygens. Tetrahedr. Lett. 30, 1749-1752 (1989).
15. Davies, H. M. L., Venkataramani, C., Hansen, T. & Hopper, D. W. New strategic reactions for organic synthesis: catalytic asymmetric C H activation to nitrogen as a surrogate for the Mannich reaction. J. Am. Chem. Soc. 125, 6462-6468 (2003).
16. Doyle, M. P., Duffy, R., Ratnikov, M. & Zhou, L. Catalytic carbene insertion into C H bonds. Chem. Rev. 110, 704-724 (2010).
17. Prier, C. K., Rankic, D. A. & MacMillan, D. W. C. Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. Chem. Rev. 113, 5322-5363 (2013).
18. Shaw, M. H., Twilton, J. & MacMillan, D. W. C. Photoredox catalysis in organic chemistry. J. Org. Chem. 81, 6898-6926 (2016).
19. Kärkäs, M. D., Porco, J. A. & Stephenson, C. R. J. Photochemical approaches to complex chemotypes: applications in natural product synthesis. Chem. Rev. 116, 9683-9747 (2016).
20. DiRocco, D. A. et al. Late-stage functionalization of biologically active heterocycles through photoredox catalysis. Angew. Chem. Int. Ed. 53, 4802-4806 (2014).
21. Zuo, Z. et al. Merging photoredox with nickel catalysis: coupling of-carboxyl sp3-carbons with aryl halides. Science 345, 437-440 (2014).
22. Zhang, X. & MacMillan, D. W. C. Alcohols as latent coupling fragments for metallaphotoredox catalysis: sp3-sp2 cross-coupling of oxalates with aryl halides. J. Am. Chem. Soc. 138, 13862-13865 (2016).
23. Roberts, B. P. Polarity-reversal catalysis of hydrogen-atom abstraction reactions: concepts and applications in organic chemistry. Chem. Soc. Rev. 28, 25-35 (1999).
24. Jeffrey, J. L., Terrett, J. A. & MacMillan, D. W. C. O-H hydrogen bonding promotes H-atom transfer from C-H bonds for C-alkylation of alcohols. Science 349, 1532-1536 (2015).
25. Shaw, M. H., Shurtleff, V. W., Terrett, J. A., Cuthbertson, J. D. & MacMillan, D. W. C. Native functionality in triple catalytic cross-coupling: sp3 C-H bonds as latent nucleophiles. Science 352, 1304-1308 (2016).
26. Lowry, M. S. et al. Single-layer electroluminescent devices and photoinduced hydrogen production from an ionic iridium(III) complex. Chem. Mater. 17, 5712-5719 (2005).
27. Durandetti, M., Devaud, M. & Périchon, J. Investigation of the reductive coupling of aryl halides and/or ethyl chloroacetate electrocatalyzed by the precursor NiX (bpy) with X = Cl, Br, or MeSO4 and bpy = 2,2-dipyridyl. New J. Chem. 20, 659-667 (1996).
28. Gutierrez, O., Tellis, J. C., Primer, D. N., Molander, G. A. & Kozlowski, M. C. Nickel-catalyzed cross-coupling of photoredox-generated radicals: uncovering a general manifold for stereoconvergence in nickel-catalyzed cross-couplings. J. Am. Chem. Soc. 137, 4896-4899 (2015).
29. Cheung, M. S., Sheong, F. K., Marder, T. B. & Lin, Z. Computational insight into nickel-catalyzed carbon-carbon versus carbon-boron coupling reactions of primary, secondary, and tertiary alkyl bromides. Chem. Eur. J. 21, 7480-7488 (2015).
30. Cernak, T., Dykstra, K. D., Tyagarajan, S., Vachal, P. & Krska, S. W. The medicinal chemist's toolbox for late stage functionalization of drug-like molecules. Chem. Soc. Rev. 45, 546-576 (2016).