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Mechanistic study of Suzuki-Miyaura cross-coupling reactions of amides mediated by [Pd(NHC)(allyl)Cl] precatalysts

(2018) CHEMCATCHEM. 10(14). p.3096-3106
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Abstract
We report a combined experimental and computational investigation of the Suzuki-Miyaura cross-coupling of amides enabled by [Pd(NHC)(allyl)Cl] precatalysts. Most crucially, mechanistic details pertaining to the Pd-0/NHC catalytic cycle were elucidated by computational methods. Mechanistic insights shed light on the role of each ligand about the metal. Sterics play a key role in the initial activation of the catalyst. As a key insight, we have shown that water participates in the activation of the Pd-NHC catalytic system. Easier activation has led to effect room temperature cross-coupling of a broad range of amides through selective N-C bond scission under the mildest conditions reported to date. The use of sterically hindered [Pd(IPr*)(cin)Cl] reported herein for the first time in the amide cross-coupling indicates that increasing flexible steric bulk of the isopropyl wingtip groups of the NHC ligand provides a modular scaffold for promoting amide cross-coupling in high yields. The precatalytic pathway involving both NHC ligands as well as the catalytic cycle beginning from the Pd-0 species are discussed. The mechanistic details provide insight into the amide bond twist (distortion) that leads to N-C cross-coupling reactions and is required for the efficient N-C bond activation.
Keywords
amides, cross-coupling reactions, density functional calculations, palladium, reaction mechanisms, N-HETEROCYCLIC CARBENES, PD-NHC PRECATALYST, ZETA VALENCE QUALITY, C BOND ACTIVATION, ROOM-TEMPERATURE, BUCHWALD-HARTWIG, ARYL CHLORIDES, GENERAL-METHOD, BASIS-SETS, SUPPORTED PRECATALYSTS

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MLA
Li, Guangchen et al. “Mechanistic Study of Suzuki-Miyaura Cross-coupling Reactions of Amides Mediated by [Pd(NHC)(allyl)Cl] Precatalysts.” CHEMCATCHEM 10.14 (2018): 3096–3106. Print.
APA
Li, G., Lei, P., Szostak, M., Casals-Cruañas, E., Poater, A., Cavallo, L., & Nolan, S. (2018). Mechanistic study of Suzuki-Miyaura cross-coupling reactions of amides mediated by [Pd(NHC)(allyl)Cl] precatalysts. CHEMCATCHEM, 10(14), 3096–3106.
Chicago author-date
Li, Guangchen, Peng Lei, Michal Szostak, Eric Casals-Cruañas, Albert Poater, Luigi Cavallo, and Steven Nolan. 2018. “Mechanistic Study of Suzuki-Miyaura Cross-coupling Reactions of Amides Mediated by [Pd(NHC)(allyl)Cl] Precatalysts.” Chemcatchem 10 (14): 3096–3106.
Chicago author-date (all authors)
Li, Guangchen, Peng Lei, Michal Szostak, Eric Casals-Cruañas, Albert Poater, Luigi Cavallo, and Steven Nolan. 2018. “Mechanistic Study of Suzuki-Miyaura Cross-coupling Reactions of Amides Mediated by [Pd(NHC)(allyl)Cl] Precatalysts.” Chemcatchem 10 (14): 3096–3106.
Vancouver
1.
Li G, Lei P, Szostak M, Casals-Cruañas E, Poater A, Cavallo L, et al. Mechanistic study of Suzuki-Miyaura cross-coupling reactions of amides mediated by [Pd(NHC)(allyl)Cl] precatalysts. CHEMCATCHEM. 2018;10(14):3096–106.
IEEE
[1]
G. Li et al., “Mechanistic study of Suzuki-Miyaura cross-coupling reactions of amides mediated by [Pd(NHC)(allyl)Cl] precatalysts,” CHEMCATCHEM, vol. 10, no. 14, pp. 3096–3106, 2018.
@article{8577730,
  abstract     = {We report a combined experimental and computational investigation of the Suzuki-Miyaura cross-coupling of amides enabled by [Pd(NHC)(allyl)Cl] precatalysts. Most crucially, mechanistic details pertaining to the Pd-0/NHC catalytic cycle were elucidated by computational methods. Mechanistic insights shed light on the role of each ligand about the metal. Sterics play a key role in the initial activation of the catalyst. As a key insight, we have shown that water participates in the activation of the Pd-NHC catalytic system. Easier activation has led to effect room temperature cross-coupling of a broad range of amides through selective N-C bond scission under the mildest conditions reported to date. The use of sterically hindered [Pd(IPr*)(cin)Cl] reported herein for the first time in the amide cross-coupling indicates that increasing flexible steric bulk of the isopropyl wingtip groups of the NHC ligand provides a modular scaffold for promoting amide cross-coupling in high yields. The precatalytic pathway involving both NHC ligands as well as the catalytic cycle beginning from the Pd-0 species are discussed. The mechanistic details provide insight into the amide bond twist (distortion) that leads to N-C cross-coupling reactions and is required for the efficient N-C bond activation.},
  author       = {Li, Guangchen and Lei, Peng and Szostak, Michal and Casals-Cruañas, Eric and Poater, Albert and Cavallo, Luigi and Nolan, Steven},
  issn         = {1867-3880},
  journal      = {CHEMCATCHEM},
  keywords     = {amides,cross-coupling reactions,density functional calculations,palladium,reaction mechanisms,N-HETEROCYCLIC CARBENES,PD-NHC PRECATALYST,ZETA VALENCE QUALITY,C BOND ACTIVATION,ROOM-TEMPERATURE,BUCHWALD-HARTWIG,ARYL CHLORIDES,GENERAL-METHOD,BASIS-SETS,SUPPORTED PRECATALYSTS},
  language     = {eng},
  number       = {14},
  pages        = {3096--3106},
  title        = {Mechanistic study of Suzuki-Miyaura cross-coupling reactions of amides mediated by [Pd(NHC)(allyl)Cl] precatalysts},
  url          = {http://dx.doi.org/10.1002/cctc.201800511},
  volume       = {10},
  year         = {2018},
}

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