Cross dehydrogenative coupling (also known as CDC reaction), coined by Chao-Jun Li of McGill University, [1] [2] [3] [4] is a type of coupling reaction allowing the construction of a carbon–carbon bond [5] or C-Heteroatom bond [6] directly from C-H bonds in the presence of an oxidant, leading to the thermodynamically unfavorable formal removal of a H2 molecule. As such, CDC are couplings belonging to the C-H activation strategy.
The key to the CDC coupling is eliminating the need for substrate prefunctionalization. Therefore, the CDC reaction has the advantages of high efficiency,
Atom economy and environmental friendliness. Such reactions can be achieved or activated by transition-metal catalysis or oxidation reaction (e.g.
benzoquinone,
peroxides,
O2,
hypervalent iodine), or by either photocatalysis or electrocatalysis. The mechanism and reactivity of the CDC reactions varies dramatically depending on the substrate.
[7]
[8] CDC reactions have been used to construct bonds between sp3-sp3, sp3-sp2, sp3-sp, sp2-sp2, sp2-sp and sp-sp C-H bonds.
[9]
[10] The synthesis and functionalization of various nitrogen, oxygen and sulfur-containing
heterocycles have also been achieved via CDC.
[11]
See also
References
- ^ Li, Chao-Jun (2009-02-17). "Cross-Dehydrogenative Coupling (CDC): Exploring C−C Bond Formations beyond Functional Group Transformations". Accounts of Chemical Research. 42 (2): 335–344. doi: 10.1021/ar800164n. ISSN 0001-4842. PMID 19220064.
- ^ Li, Z.; Bohle, D. S.; Li, C.-J. (2006-06-13). "Cu-catalyzed cross-dehydrogenative coupling: A versatile strategy for C-C bond formations via the oxidative activation of sp3 C-H bonds". Proceedings of the National Academy of Sciences. 103 (24): 8928–8933. Bibcode: 2006PNAS..103.8928L. doi: 10.1073/pnas.0601687103. ISSN 0027-8424. PMC 1482542. PMID 16754869.
- ^ "Cross-Dehydrogenative Coupling". Chemistry LibreTexts. 2016-12-17. Retrieved 2020-10-22.
- ^ Li, Chao-Jun, ed. (2014). From C-H to C-C Bonds. Green Chemistry Series. doi: 10.1039/9781782620082. ISBN 978-1-84973-797-5. ISSN 1757-7047.
- ^ Yeung, Charles S.; Dong, Vy M. (2011-03-09). "Catalytic Dehydrogenative Cross-Coupling: Forming Carbon−Carbon Bonds by Oxidizing Two Carbon−Hydrogen Bonds". Chemical Reviews. 111 (3): 1215–1292. doi: 10.1021/cr100280d. ISSN 0009-2665. PMID 21391561.
- ^ Krylov, Igor B.; Vil’, Vera A.; Terent’ev, Alexander O. (2015-01-20). "Cross-dehydrogenative coupling for the intermolecular C–O bond formation". Beilstein Journal of Organic Chemistry. 11 (1): 92–146. doi: 10.3762/bjoc.11.13. ISSN 1860-5397. PMC 4311763. PMID 25670997.
- ^ Tsang, Althea S.-K.; Park, Soo J.; Todd, Matthew H. (2014), Li, Chao-Jun (ed.), CHAPTER 11. Mechanisms of Cross-Dehydrogenative-Coupling Reactions, Green Chemistry Series, Cambridge: Royal Society of Chemistry, pp. 254–294, doi: 10.1039/9781782620082-00254, ISBN 978-1-84973-797-5, retrieved 2020-10-22
- ^ Huang, Chia-Yu; Kang, Hyotaik; Li, Jianbin; Li, Chao-Jun (2019-10-18). "En Route to Intermolecular Cross-Dehydrogenative Coupling Reactions". The Journal of Organic Chemistry. 84 (20): 12705–12721. doi: 10.1021/acs.joc.9b01704. ISSN 0022-3263. PMID 31441304. S2CID 201617266.
- ^ Girard, Simon A.; Knauber, Thomas; Li, Chao-Jun (2014-01-03). "The Cross-Dehydrogenative Coupling of C sp 3H Bonds: A Versatile Strategy for CC Bond Formations". Angewandte Chemie International Edition. 53 (1): 74–100. doi: 10.1002/anie.201304268. PMID 24214829.
- ^ Scheuermann, Caroline J. (2010-03-01). "Beyond Traditional Cross Couplings: The Scope of the Cross Dehydrogenative Coupling Reaction". Chemistry: An Asian Journal. 5 (3): 436–451. doi: 10.1002/asia.200900487. PMID 20041458.
- ^ Srivastava, Ananya; Jana, Chandan K., eds. (2019). Heterocycles via Cross Dehydrogenative Coupling: Synthesis and Functionalization. Singapore: Springer Singapore. doi: 10.1007/978-981-13-9144-6. ISBN 978-981-13-9143-9. S2CID 201623590.