Next Article in Journal
Designing the Hotspots Distribution by Anisotropic Growth
Next Article in Special Issue
Dendrimers Functionalized with Palladium Complexes of N-, N,N-, and N,N,N-Ligands
Previous Article in Journal
Progress in the Application of Nanoparticles and Graphene as Drug Carriers and on the Diagnosis of Brain Infections
Previous Article in Special Issue
Synthesis and Biological Studies on Dinuclear Gold(I) Complexes with Di-(N-Heterocyclic Carbene) Ligands Functionalized with Carbohydrates
Article

Transamidation of Amides and Amidation of Esters by Selective N–C(O)/O–C(O) Cleavage Mediated by Air- and Moisture-Stable Half-Sandwich Nickel(II)–NHC Complexes

Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, USA
*
Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Academic Editor: Derek J. McPhee
Molecules 2021, 26(1), 188; https://doi.org/10.3390/molecules26010188
Received: 10 December 2020 / Revised: 23 December 2020 / Accepted: 24 December 2020 / Published: 2 January 2021
The formation of amide bonds represents one of the most fundamental processes in organic synthesis. Transition-metal-catalyzed activation of acyclic twisted amides has emerged as an increasingly powerful platform in synthesis. Herein, we report the transamidation of N-activated twisted amides by selective N–C(O) cleavage mediated by air- and moisture-stable half-sandwich Ni(II)–NHC (NHC = N-heterocyclic carbenes) complexes. We demonstrate that the readily available cyclopentadienyl complex, [CpNi(IPr)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), promotes highly selective transamidation of the N–C(O) bond in twisted N-Boc amides with non-nucleophilic anilines. The reaction provides access to secondary anilides via the non-conventional amide bond-forming pathway. Furthermore, the amidation of activated phenolic and unactivated methyl esters mediated by [CpNi(IPr)Cl] is reported. This study sets the stage for the broad utilization of well-defined, air- and moisture-stable Ni(II)–NHC complexes in catalytic amide bond-forming protocols by unconventional C(acyl)–N and C(acyl)–O bond cleavage reactions. View Full-Text
Keywords: transamidation; twisted amides; NHCs; N-heterocyclic carbenes; nickel; Buchwald–Hartwig; amidation; cyclopentadienyl; nickel–NHCs; amide bonds; N–C activation; [CpNi(NHC)X] transamidation; twisted amides; NHCs; N-heterocyclic carbenes; nickel; Buchwald–Hartwig; amidation; cyclopentadienyl; nickel–NHCs; amide bonds; N–C activation; [CpNi(NHC)X]
Show Figures

Figure 1

MDPI and ACS Style

Buchspies, J.; Rahman, M.M.; Szostak, M. Transamidation of Amides and Amidation of Esters by Selective N–C(O)/O–C(O) Cleavage Mediated by Air- and Moisture-Stable Half-Sandwich Nickel(II)–NHC Complexes. Molecules 2021, 26, 188. https://doi.org/10.3390/molecules26010188

AMA Style

Buchspies J, Rahman MM, Szostak M. Transamidation of Amides and Amidation of Esters by Selective N–C(O)/O–C(O) Cleavage Mediated by Air- and Moisture-Stable Half-Sandwich Nickel(II)–NHC Complexes. Molecules. 2021; 26(1):188. https://doi.org/10.3390/molecules26010188

Chicago/Turabian Style

Buchspies, Jonathan, Md. M. Rahman, and Michal Szostak. 2021. "Transamidation of Amides and Amidation of Esters by Selective N–C(O)/O–C(O) Cleavage Mediated by Air- and Moisture-Stable Half-Sandwich Nickel(II)–NHC Complexes" Molecules 26, no. 1: 188. https://doi.org/10.3390/molecules26010188

Find Other Styles
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Back to TopTop