The reaction between g-azido-N-tosylhydrazones and boronic acids leads to the obtention of 2,2-disubstituted pyrrolidines in adomino process that includes 1) diazoalkane formation, 2) intermolecular carboborylation of the diazocompound, and 3) intramolecular carborylation of the azide, and comprises the formation of aC sp 3 À Csp 3 and aC sp 3 À N bonds on the same carbon atom. The reaction proceeds without the need of any transition-metal catalyst under microwave activation and features wide scope in both reaction partners.It can be applied to both alkyla nd arylboronic acids with equal efficiency.W ith N-tosylhydrazones derived from 2-(2-azidoethyl)-cyclopentanone and cyclohexanone the reactions are highly diastereoselective leading to the cis-fused bicyclic systems as unique diastereoisomers.T he scope of the process is illustrated by over sixty examples,including scaffolds present in natural alkaloids,and the mechanistic proposal is suppported by DFT-based computations.

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Benzothiazole-2-carbaldehyde or 6-nitrobentothiatole-2-carbaldehyde can be used for the synthesis of aldehydes or ketones starting from the corresponding amines via transaminations. The method has wide applications and the yields are generally greater than 80%. Bari, Italy

The reactions of N-sulfonylhydrazones derived from cyclic ketones with g-azidopropylboronic acid and 2-(azidomethyl)phenylboronic acid give rise to spirocyclic pyrrolidines and spiroisoindolines,r espectively.T he reactions proceed without the need of any transition-metal catalyst through adomino process that comprises the formation of aCsp 3 -C and aCsp 3 -N bond of the former hydrazonic carbon. The scope of the reaction has been explored by the preparation of over 50 examples of NH-unprotected spirocyclic derivatives.I mportantly,this methodology could be applied for the preparation of alkaloid steroids from steroid N-tosylhydrazones.

The reaction between g-azido-N-tosylhydrazones and boronic acids leads to the obtention of 2,2-disubstituted pyrrolidines in adomino process that includes 1) diazoalkane formation, 2) intermolecular carboborylation of the diazocompound, and 3) intramolecular carborylation of the azide, and comprises the formation of aC sp 3 À Csp 3 and aC sp 3 À N bonds on the same carbon atom. The reaction proceeds without the need of any transition-metal catalyst under microwave activation and features wide scope in both reaction partners.It can be applied to both alkyla nd arylboronic acids with equal efficiency.W ith N-tosylhydrazones derived from 2-(2-azidoethyl)-cyclopentanone and cyclohexanone the reactions are highly diastereoselective leading to the cis-fused bicyclic systems as unique diastereoisomers.T he scope of the process is illustrated by over sixty examples,including scaffolds present in natural alkaloids,and the mechanistic proposal is suppported by DFT-based computations.