This report describes a unique Pd-catalyzed oxidative carboamination of protected aminoalkenes in which inexpensive unactivated nucleophilic arenes are incorporated to give carboamination products in good yields. A variety of protected amide and carbamate groups are tolerated, and various five-, six-, and seven-membered rings are formed in good yields. Under these conditions, halobenzenes are activated at the C-H bond rather than the C-X bond, and very high regioselectivity for the para substitution product is observed in all cases. We propose that this carboamination takes place via electrophilic aromatic substitution of a Pd(IV) alkyl intermediate.
A Pd-catalyzed alkoxyamination of protected aminoalkenes promoted by N-fluorobenzenesulfonimide is described. This mild transformation allows the direct formation of ethers from carbon-carbon double bonds. An unusual switch from exo to endo selectivity in polar solvents was discovered, allowing the selective formation of either regioisomer by careful choice of reaction conditions.
Ring closure reactions O 0130Palladium-Catalyzed Carboamination of Alkenes Promoted by N-Fluorobenzenesulfonimide via C-H Activation of Arenes. -A novel method is presented for the intramolecular amination of aminoolefins, e.g. (I), using N-fluorobenzenesulfonimide as oxidant in the presence of weakly nucleophilic arenes. A variety of five-, six-and seven-membered azacycles (III), (V), (VIII), (X) and (XII) is formed in moderate yields. -(ROSEWALL, C. F.; SIBBALD, P. A.; LISKIN, D. V.; MICHAEL*, F. E.; J. Am. Chem. Soc. 131 (2009) 27, 9488-9489; Dep. Chem., Univ. Wash., Seattle, WA 98195, USA; Eng.) -Mischke 50-030
The Pd/ fluorobenzenesulfonimide‐mediated treatment of 5 aminopentenes with alcohols and AcOH allows a mild access to pyrrolidines like (III), (VI), and (IX).
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