Jianxin Chen

A novel and practical asymmetric synthetic method of α‐amino amides by the reaction between N‐sulfonyl imines and N‐methyl‐N‐R‐(1‐phenyl)ethylcarbamoyl (trimethyl)silane under the induction of chiral group has been developed. The protocol tolerates various N‐sulfonyl imines bearing different groups, including aryl, double bond conjugated aryl, heteroaryl, and aliphatic group. Using carbamoylsilane with chiral group, the diastereoselectivity was very high for reactions of most N‐sulfonyl imines, and only one diastereomer was afforded in many reactions.

Direct aminocarbonylation of β-nitroalkenes bearing β-positioned ethoxycarbonyl group using carbamoylsilane as an amide source afforded β-nitro amide derivatives under mild conditions without use of catalysts.

A novel and practical method has been developed for the preparation of α-keto amides by a catalyst-free aminocarbonylation of carboxylic esters with N,N-dimethylcarbamoyl(trimethyl)silane under neutral conditions. A new protocol for the synthesis of vicinal tricarbonyl compounds was also developed by using this method. In the case of diesters, only one ester group reacted selectively with 1.2 equivalents of the carbamoylsilane, leading to the formation of a single α-keto amide. The reaction was suitable for aryl, hetaryl, or open-chain esters containing strongly electron-withdrawing groups.

A nickel‐catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source leading to corresponding secondary or primary aromatic amides has been developed, in which the methoxymethyl and benzyl were used as amino protecting group. The protocol tolerates a broad range of aryl halides bearing different functional groups to afford good yields of aryl amides under mild reaction conditions. The types and the relative positions of substituents on the aryl ring make a notable impact on the coupling efficiency. The plausible mechanism of nickel‐catalyzed aminocarbonylation has been suggested.

The reaction of carbamoylsilanes with oxetan-3-one under anhydrous conditions in toluene at 60 °C affords 3-silyloxyor 3-hydroxyoxetane-3-carboxamides in good yields.

A convenient synthetic method for vicinal tricarbonyl amides by the cross-coupling reaction of α-oxo acid chlorides with carbamoylsilanes is developed. The reaction tolerates a broad range of substituents on the amido nitrogen of carbamoylsilanes, and directly affords good yields of vicinal tricarbonyl amides under mild conditions without use of oxidants. The reaction of carbamoylsilanes with oxalyl chloride has also been explored, and is accompanied by decarbonylation to give vicinal tricarbonyl amides.

Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium–catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.