KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
KAUST Grant NumberURF/1/3030-01
Online Publication Date2019-04-29
Print Publication Date2019-12
Permanent link to this recordhttp://hdl.handle.net/10754/652835
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AbstractTransition-metal-catalyzed cross-couplings have been extensively used in the pharmaceutical and agrochemical industries for the construction of diverse C-C bonds. Conventional cross-coupling reactions require reactive electrophilic coupling partners, such as organohalides or sulfonates, which are not environmentally friendly and not naturally abundant. Another disadvantage associated with these transformations is the need for an exogenous base to facilitate the key transmetalation step, and this reagent inevitably induces side reactions and limits the substrate scope. Here, we report an unconventional Suzuki-type approach to the synthesis of biaryls, through nickel-catalyzed deformylative cross coupling of aldehydes with organoboron reagents under base-free conditions. The transformation tolerates structurally diverse (hetero)aryl substituents on both coupling partners and shows high reactivity and excellent functional group tolerance. Furthermore, the protocol was carried out on gram scale and successfully applied to the functionalization of complex biologically active molecules. Mechanistic investigations support a catalytic cycle involving the oxidative addition of the nickel into the aldehyde C(acyl)-H bond with subsequent hydride transfer, transmetalation, decarbonylation and reductive elimination processes.
CitationGuo L, Srimontree W, Zhu C, Maity B, Liu X, et al. (2019) Nickel-catalyzed Suzuki–Miyaura cross-couplings of aldehydes. Nature Communications 10. Available: http://dx.doi.org/10.1038/s41467-019-09766-x.
SponsorsL.G. acknowledges the support from the China Scholarship Council. C.Z., B.M., L.C., and M.R. acknowledge King Abdullah University of Science and Technology (KAUST) for support and the KAUST Supercomputing Laboratory for providing the computational resources of the supercomputer Shaheen II. This research was supported by King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research under award number URF/1/3030-01.