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• 624-31-7 4-tolyl iodide 
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Relevant academic research and scientific papers

Palladium-Catalyzed Carbonylative Cyclization of Amines via γ-C(sp3)-H Activation: Late-Stage Diversification of Amino Acids and Peptides

The selective γ-C(sp3)-H carbonylation of N-(2-pyridyl)sulfonyl (N-SO2Py)-protected amines has been accomplished by using palladium catalysis and Mo(CO)6 as carbonyl source. The reaction provides a powerful approach for derivatization of amine-based moieties, including amino acids, into richly functionalized γ-lactams. Not only methyl groups, but also methylene C-H bonds of cyclopropanes and conformationally biased molecules can be activated to provide ring-fused γ-lactam derivatives. This carbonylation protocol is also amenable to the late-stage diversification of more-complex multifunctional molecules such as dipeptides and tripeptides, demonstrating the key role of the N-SO2Py as directing group and its capacity to override other inherent substrate coordinating elements. In addition to providing an attractive solution to the difficulties in handling hazardous CO gas, the use of Mo(CO)6 as an air-stable solid source of CO in substoichiometric amount (0.33 equiv) ensures PdII-catalytic activity by preventing its decomposition or deactivation under excess of CO via reduction of PdII to Pd0 or saturation of the metal coordination sphere. Indeed, significantly lower efficiency is observed when the reactions are carried out under CO atmosphere (1 atm), or in the presence of increased amounts of Mo(CO)6. A series of experimental and DFT mechanistic studies provide important insights about the reaction mechanism.

Experimental and computational studies on the mechanism of the Pd-catalyzed C(sp3)-H γ-arylation of amino acid derivatives assisted by the 2-pyridylsulfonyl group

The Pd(OAc)2-catalyzed γ-arylation of amino acid esters bearing a removable N-(2-pyridyl)sulfonyl directing group via C(sp 3)-H activation provides a direct method to form functionalized amino acids without racemization at the α-C an

Palladium-catalyzed N-(2-pyridyl)sulfonyl-directed C(sp3)-H γ-arylation of amino acid derivatives

The direct Pd-catalyzed γ-arylation of amino acid esters bearing a removable N-(2-pyridyl)sulfonyl directing group is described. A variety of N-(2-pyridyl)sulfonamide amino acid derivatives, including α-quaternary amino acid and β-amino acid substrates, react with iodoarenes in the presence of Pd(OAc)2 to provide γ-arylated products in synthetically useful yields. An unprecedented remote C(sp3)-H arylation of dipeptides is presented, illustrating the compatibility of the method with the presence of the peptidic bond. The process occurs without racemization at the Cα center and the auxiliary controlling group can be easily installed and removed in the amino acid backbone. A bimetallic Pd II γ-metalated complex has been isolated and characterized showing the key role exerted by the (2-pyridyl)sulfonyl unit.