Palladium and TEMPO as Co‐Catalysts in a Desulfinative Homocoupling Reaction

Ortgies, Dirk H.; Chen, Fei; Forgione, Pat

doi:10.1002/ejoc.201402134

Cited by 22 publications

(5 citation statements)

References 63 publications

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“…Given that phenylsulfinic acid has been shown to readily undergo desulfination by palladium complexes in both the gas-phase [24] and in synthetic protocols, [30,31] here we demonstrate that while the desired palladium-mediated ExIn mechanism operates in the gasphase (Scheme 1c, Eqns 1, 2), a palladium-mediated biaryl coupling side reaction dominates in solution. [32][33][34][35]…”

Section: Introductionmentioning

confidence: 99%

Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration

Yang

Canty²,

O’Hair³

2022

Aust. J. Chem.

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The gas-phase extrusion-insertion (ExIn) reactions of the palladium complexes [(phen) n Pd (O 2 SC 6 H 5 )] + (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MS n ) experiments consisting of electrospray ionisation and a linear ion trap combined with density functional theory (DFT) calculations. Desulfination of palladium sulfinate cations under collision-induced dissociation (CID) generates the organopalladium intermediates [(phen) n Pd(C 6 H 5 )] + . Of these two organometallic cations, only [(phen)Pd(C 6 H 5 )] + reacts with phenyl isocyanate via insertion to yield [(phen)Pd(NPhC(O)C 6 H 5 )] + . The formation of a coordinated amidate anion is supported by DFT calculations. In exploring this reactivity in the solution phase, we found that heating a mixture of benzenesulfinic acid, phenylisocyanate and palladium trifluoroacetate under a range of different conditions (ligand free versus with ligand, different solvents, addition of acid or base) failed to lead to the formation N-phenyl-benzamide in all cases. Instead, biphenyl was formed and could be isolated in a yield of 46%. DFT calculations using a solvent continuum reveal that the barrier associated with the insertion reaction lies above the competing sequential reactions of desulfination of a second phenyl sulfinate followed by reductive elimination of biphenyl.

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Section: Introductionmentioning

confidence: 99%

Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration

Yang

Canty²,

O’Hair³

2022

Aust. J. Chem.

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“…Decarboxylative dimerization of arylcarboxylic acids was reported by Cornella et al with limited substrate universality under harsh conditions (Scheme , C─C cleavage). Desulfitative homocoupling of arylsulfonyl compounds has drawn much attention for their higher reactivities under milder conditions than corresponding arylcarboxylic acids (Scheme , C─S cleavage) . However, the generation of environmentally detrimental sulfur dioxide was unavoidable.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐catalyzed reductive homocoupling of aryl sulfonates via cleavage of C─O bond at room temperature

Zhong

Chen²,

Liu³

et al. 2017

Applied Organom Chemis

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Palladium‐catalyzed reductive homocoupling of aryl sulfonates has been successfully achieved under mild conditions. This transformation is a new method for the homocoupling reaction of aryl sulfonates at room temperature via the cleavage of C─O bonds, thus providing an alternative synthesis of symmetric biaryls. The reported reductive homocoupling reaction is tolerant of many common functional groups regardless of electron‐donating or electron‐withdrawing nature, making this newly developed transformation important for complementing Ullmann coupling. Experimental Section. Typical procedure for the products.

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“…The remaining challenges in the field are discussed in the General Conclusion and Perspectives. This review focuses on the direct arylation or alkylation using AlkSO 2 R or ArSO 2 R derivatives as the coupling partners; however, it should be mentioned that ArSO 2 R derivatives have also been used in several other coupling processes, such as Mizoroki–Heck, − Suzuki–Miyaura, , Corriu–Kumada, Sonogashira, and also several other metal-catalyzed desulfitative cross-coupling reactions. − …”

Section: Introductionmentioning

confidence: 99%

Functionalization of C–H Bonds via Metal-Catalyzed Desulfitative Coupling: An Alternative Tool for Access to Aryl- or Alkyl-Substituted (Hetero)arenes

2015

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Palladium and TEMPO as Co‐Catalysts in a Desulfinative Homocoupling Reaction

Abstract: A range of aryl sulfinates can be oxidatively dimerized to generate substituted biphenyls with concomitant extrusion of sulfur dioxide with a palladium catalyst. Catalytic amounts of TEMPO and excess oxygen are utilized as oxidants to regenerate the palladium catalyst.

Cited by 22 publications

References 63 publications

Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration

Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration

Palladium‐catalyzed reductive homocoupling of aryl sulfonates via cleavage of C─O bond at room temperature

Functionalization of C–H Bonds via Metal-Catalyzed Desulfitative Coupling: An Alternative Tool for Access to Aryl- or Alkyl-Substituted (Hetero)arenes

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