A single‐step synthesis of N‐aryl‐N′‐tosyldiazenes from primary aromatic amines was developed. A wide range of aromatic amines provided the corresponding products in high yields by N–N bond formation with RhII–nitrene intermediates, which were generated in situ from dirhodium(II) complex catalysts and (tosylimino)‐2,4,6‐trimethylphenyliodinane, followed by oxidation. The synthesized N‐aryl‐N′‐tosyldiazenes were successfully demonstrated to serve as potent and stable surrogates for diazonium salts in the two‐step deaminative transformation of primary aromatic amines.

Rh(ii)-Nitrene-mediated N–H amination of 2-aminophenylboronates triggered a cascade of oxidation/elimination processes resulting in the generation of benzynes.

An iterative Ni-catalyzed C(sp 3 )ÀC(sp 3 ) cross-coupling reaction of a novel cis-cyclopropane containing bifunctional building blocks with alkyl halides and alkyl Grignard reagents enabled the introduction of a cyclopropane ring into the desired position(s) of saturated carbon frameworks, providing a straightforward synthetic route to cyclopropane fatty acids. The present method creates a direct route for the construction of saturated carbon frameworks, and can avoid the tedious multistep operations based on unsaturated functional group manipulations that are often employed in conventional synthetic routes. This method could be applicable to the synthesis of trans-cyclopropane fatty acids and enantioenriched cyclopropane fatty acids. Formal synthesis of a-mycolic acid was achieved by the C(sp 3 )ÀC(sp 3 ) cross-coupling reaction of cyclopropane-containing bifunctional building blocks. Scheme 2. Synthetic routes of alkyl chains including a cyclopropane ring. Scheme 3. Synthesis of CFAs using a cyclopropane-containing building block.Scheme 4. Synthesis of cis-cyclopropane-containing building block 7.UPDATES