937-23-5

Upstream product

• 6911-87-1 4-bromo-N-methylaniline 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 100-61-8 N-methylaniline 
• 544-16-1 n-Butyl nitrite 
• 60-29-7 diethyl ether 
• 64-17-5 ethanol 
• 614-00-6 N-methyl-N-nitrosoaniline 
• 10035-10-6 hydrogen bromide 
• 7782-77-6 cis-nitrous acid 
• 7647-01-0 hydrogenchloride 
• 106-40-1 4-bromo-aniline 
• 509-14-8 tetranitromethane 

Downstream Products

• 50438-47-6 N-(4-bromo-phenyl)-N-methylacetamide 
• 6911-87-1 4-bromo-N-methylaniline 
• 74763-71-6 1-(4-bromophenyl)-1-methylhydrazine 
• 848749-78-0 5-bromo-1,3-dimethyl-2-phenyl-1H-indole 
• 106874-91-3 5-bromo-2-(methylamino)benzonitrile 
• 39573-20-1 (5-bromo-2-(methylamino)phenyl)(phenyl)methanone 
• 114202-80-1 D-arabino-[2]hexosulose-bis-[(4-bromo-phenyl)-methyl-hydrazone] 

Relevant academic research and scientific papers

One-Pot Tandem ortho-Naphthoquinone-Catalyzed Aerobic Nitrosation of N-Alkylanilines and Rh(III)-Catalyzed C-H Functionalization Sequence to Indole and Aniline Derivatives

The nitroso group served as a traceless directing group for the C-H functionalization of N-alkylanilines, ultimately removed after functioning either as an internal oxidant or under subsequent reducing conditions. The unique ability of o-NQ catalysts to aerobically oxidize the N-alkylanilines without using solvents and stoichiometric amounts of oxidants has rendered the new opportunity to develop the telescoped catalyst systems without a need for directly handling the hazardous N-nitroso compounds.

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.

Rh(iii)-catalyzed, hydrazine-directed C-H functionalization with 1-alkynylcyclobutanols: A new strategy for 1: H -indazoles

Rh(iii)-catalyzed coupling of phenylhydrazines with 1-alkynylcyclobutanols was realized through a hydrazine-directed C-H functionalization pathway. This [4+1] annulation, based on the cleavage of a Csp-Csp triple bond in alkynylcyclobutanol, provides a new pathway to prepare diverse 1H-indazoles under mild reaction conditions. This journal is

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-catalyzed oxidative C-H/C-H cross-coupling of aniline with heteroarene: N-nitroso group enabled mild conditions

The development of transition metal-catalyzed oxidative C-H/C-H cross-coupling between two (hetero)arenes to forge aryl-heteroaryl motifs under mild conditions is an appealing yet challenging task. Herein, we disclose a rhodium-catalyzed oxidative C-H/C-H cross-coupling reaction of an N-nitrosoaniline with a heteroarene under mild conditions. The judicious choice of the N-nitroso group as a directing group enables heightened reactivity. The coupled products could be transformed expediently to (2-aminophenyl)heteroaryl skeletons.

Highly selective sp3 C-N bond activation of tertiary anilines modulated by steric and thermodynamic factors

A highly selective sp3 C-N cleavage of tertiary anilines was achieved using the TBN/TEMPO catalyst system. When N,N-diaklylanilines (alkyl, benzyl) were employed, the N-CH3 bond was selectively cleaved via radical C-H activation. Moreover, when the allyl group was installed, totally reverse selectivity was observed. It is worth noting that the solvent effect is also crucial to obtain high reaction efficiency and selectivity.

Palladium-catalyzed ortho-acylation of N-Nitrosoanilines with α-oxocarboxylic acids: A convenient method to synthesize N-Nitroso ketones and indazoles

An efficient and mild protocol for regioselective synthesis of N-Nitroso aryl ketones by palladium-catalyzed direct acylation of arenes using N-Nitroso as directing groups is described. This reaction proceeded smoothly and could tolerate a variety of functional groups. Moreover, this chemistry offers a convenient access to a range of indazoles.

Copper(II)-catalyzed oxidative N-nitrosation of secondary and tertiary amines with nitromethane under an oxygen atmosphere

The combination of a catalytic amount of Cu(OTf)2 and less than a stoichiometric amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under an O2 atmosphere effectively promoted the N-nitrosation of both secondary aromatic/aliphatic amines and tertiary aromatic amines with nitromethane (CH3NO2) leading to the preparation of N-nitrosamine derivatives.

Palladium-catalyzed oxidative C-H bond acylation of N-nitrosoanilines with toluene derivatives: A traceless approach to synthesize N-alkyl-2-aminobenzophenones

A palladium-catalyzed cascade cross-coupling of N-nitroso-anilines and toluene derivatives for the direct synthesis of N-alkyl-2-aminobenzophenones is described. N-nitroso groups in anilines can act as the traceless directing groups while toluene derivatives can serve as effective acyl precursors under mild reaction conditions.

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.