Palladium-catalyzed formation of oxazolidinones from biscarbamates: a mechanistic study

Abstract

SummaryOxazolidinones can be synthesized starting from cyclic biscarbamates via a palladium-catalyzed reaction. To test the proposed mechanism of this reaction, first, bicyclonorcarene endoperoxides derived from cyano and carbomethoxy cycloheptatrienes were synthesized and converted into the corresponding diols. The reaction of diols with toluenesulfonyl isocyanate followed by a palladium catalyzed reaction furnished oxazolidinone derivatives in similar yields. It was shown that, if one face of the double bond is blocked by substituents such as H or CN, the reaction also takes place. On the basis of these results, it was assumed that an antiperiplanar orientation of the metal and nucleophile is not necessary to form oxazolidinones. The metal is probably bonded to the allylic system from the same face as the nucleophile.

Kinetic Separation and Asymmetric Reactions of Norcaradiene Cycloadducts: Facilitated Access via H2O-Accelerated Cycloaddition

“…Desymmetrization of the meso- diol was then accomplished via condensation with p -toluenesulfonyl isocyanate to provide the bis-carbamate 15 in 87% yield from 8a . Selective π-allyl displacement of the enantiotopic carbamates under Pd catalysis afforded the protected 1,2- syn -amino alcohol 16 . Extension of this methodology to enantioselective methods is well-precedented …”