1978-27-4

Upstream product

• 1978-38-7 2-fluoro-N-methylaniline 

Downstream Products

• 1416897-48-7 (E)-methyl 3-(3-fluoro-2-(methyl(nitroso)amino)phenyl)acrylate 
• 1978-53-6 1-(2-fluorophenyl)-1-methylhydrazine 

Relevant academic research and scientific papers

Rhodium-catalyzed tandem acylmethylation/annulation ofN-nitrosoanilines with sulfoxonium ylides for the synthesis of substituted indazoleN-oxides

An atom-economical protocol for synthesizing indazoleN-oxides from readily availableN-nitrosoanilines and sulfoxonium ylides through the rhodium(iii)-catalyzed C-H activation and cyclization reaction is described here. This protocol employs nitroso as a traceless directing group. The transformation features powerful reactivity, tolerates various functional groups, and proceeds with moderate to good yields under an ambient atmosphere, providing a straightforward approach to access structurally diverse and valuable indazoleN-oxide derivatives. Importantly, this new annulation process represents a hitherto unobserved reactivity pattern for theN-nitroso group.

Cp?Rh(iii) catalyzed: Ortho -halogenation of N -nitrosoanilines by solvent-controlled regioselective C-H functionalization

We present a novel, efficient, and regioselective method for the rhodium-catalyzed direct C-H ortho-halogenation of anilines that involves a removable N-nitroso directing group. This method featured mild reaction conditions, wide substrate scope, good functional group tolerance and satisfactory yields. To maintain the high ortho-regioselectivity and conversion, increasing the steric hindrance of the solvent was critical. Preliminary mechanistic studies suggest that C-H activation may be involved in the rate-determining step.

Rhodium(III)-Catalyzed Directed C?H Amidation of N-Nitrosoanilines and Subsequent Formation of 1,2-Disubstituted Benzimidazoles

An efficient rhodium-catalyzed direct C?H amidation of N-nitrosoanilines with 1,4,2-dioxazol-5-ones as amidating agents has been developed. This method featured mild reaction conditions, a wide substrate scope and satisfactory yields. Besides, the amidated products could be readily converted to pharmaceutically valuable 1,2-disubstituted benzimidazoles via an HCl-mediated deprotection/cyclization process in one pot.

Rhodium(III)-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate for cycloaddition/fragmentation synthesis of indazoles

RhIII-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N-nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C-H functionalization-based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tri-cyclic-fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.

Rhodium(III)-catalyzed N-nitroso-directed C-H olefination of arenes. High-yield, versatile coupling under mild conditions

N-Nitroso compounds are a versatile class of organic structures that allow expedient access to a diversity of synthetically useful architectures through demonstrated reactivities. We report herein the development of a Rh(III)-catalyzed N-nitroso-directed