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[Pd(NHC)(μ-Cl)Cl]2: Versatile and Highly Reactive Complexes for Cross-Coupling Reactions that Avoid Formation of Inactive Pd(I) Off-Cycle Products
- Source :
- iScience, 2020, vol. 23, núm. 8, art.núm.101377, Articles publicats (D-Q), DUGiDocs – Universitat de Girona, instname, iScience, iScience, Vol 23, Iss 8, Pp 101377-(2020), ISCIENCE
- Publication Year :
- 2020
- Publisher :
- Elsevier, 2020.
-
Abstract
- Summary The development of more reactive, general, easily accessible, and readily available Pd(II)–NHC precatalysts remains a key challenge in homogeneous catalysis. In this study, we establish air-stable NHC–Pd(II) chloro-dimers, [Pd(NHC)(μ-Cl)Cl]2, as the most reactive Pd(II)–NHC catalysts developed to date. Most crucially, compared with [Pd(NHC)(allyl)Cl] complexes, replacement of the allyl throw-away ligand with chloride allows for a more facile activation step, while effectively preventing the formation of off-cycle [Pd2(μ-allyl)(μ-Cl)(NHC)2] products. The utility is demonstrated via broad compatibility with amide cross-coupling, Suzuki cross-coupling, and the direct, late-stage functionalization of pharmaceuticals. Computational studies provide key insight into the NHC–Pd(II) chloro-dimer activation pathway. A facile synthesis of NHC–Pd(II) chloro-dimers in one-pot from NHC salts is reported. Considering the tremendous utility of Pd-catalyzed cross-coupling reactions and the overwhelming success of [Pd(NHC)(allyl)Cl] precatalysts, we believe that NHC–Pd(II) chloro-dimers, [Pd(NHC)(μ-Cl)Cl]2, should be considered as go-to precatalysts of choice in cross-coupling processes.<br />Graphical Abstract<br />Highlights • Highly reactive, air-stable PdII–NHC chloro-dimer catalysts for cross-coupling reactions • Broad substrate scope, excellent functional group tolerance, and chemoselectivity • Rapid one-step catalyst synthesis and facile catalyst activation • DFT studies provide key insights into PdII–NHC chloro-dimer activation pathway<br />Chemistry; Inorganic Chemistry; Catalysis; Organic Synthesis
- Subjects :
- 0301 basic medicine
Catalitzadors
chemistry.chemical_element
Catàlisi homogènia
Homogeneous catalysis
02 engineering and technology
PRECATALYST
Coupling reaction
Article
Catalysis
Inorganic Chemistry
03 medical and health sciences
chemistry.chemical_compound
TEMPERATURE SUZUKI-MIYAURA
Amide
QD
lcsh:Science
BASIS-SETS
Multidisciplinary
Catalysts
Ligand
PALLADIUM
DERIVATIVES
Aryl
Organic Synthesis
DAS
QD Chemistry
021001 nanoscience & nanotechnology
Combinatorial chemistry
Chemistry
030104 developmental biology
chemistry
HETEROCYCLIC CARBENE COMPLEXES
GENERAL-METHOD
CHLORIDES
Organic synthesis
lcsh:Q
0210 nano-technology
(NHC)PD(ALLYL)CL NHC
ARYL
Palladium
APPROXIMATION
Subjects
Details
- ISSN :
- 25890042
- Database :
- OpenAIRE
- Journal :
- iScience, 2020, vol. 23, núm. 8, art.núm.101377, Articles publicats (D-Q), DUGiDocs – Universitat de Girona, instname, iScience, iScience, Vol 23, Iss 8, Pp 101377-(2020), ISCIENCE
- Accession number :
- edsair.doi.dedup.....1d5d523ab3b895be4c1ba7e5156c4337