937716-84-2

Upstream product

• 524-38-9 N-hydroxyphthalimide 
• 17933-03-8 m-tolylboronic acid 

Downstream Products

• 74993-52-5 O-(3-methylphenyl)hydroxylamine 
• 39720-17-7 2-(2'-hydroxy-4'-methylphenyl)benzoxazole 
• 13429-10-2 N-(2-hydroxy-4-methylphenyl)acetamide 
• 3098-18-8 2-hydroxy-4-methylbenzophenone 
• 14770-90-2 2,3-diphenyl-6-methylbenzofuran 
• 1443440-55-8 N-(m-tolyloxy)acetamide 

Relevant academic research and scientific papers

Synthesis of ortho-phenolic sulfilimines via an intermolecular sulfur atom transfer cascade reaction

To expand the toolbox for the synthesis of ortho-phenolic sulfilimines, sigmatropic rearrangements were introduced to the field of sulfilimine chemistry. Herein we report a N-H sulfenylation/[2,3]-sigmatropic rearrangement cascade reaction. This mild reaction enables commercially available thiols to serve as the sulfenylation reagent and generates water as the sole byproduct. Moreover, the reaction has a wide substrate scope and can be conducted on a gram scale with excellent reaction efficiency.

Dual Directing-Groups-Assisted Redox-Neutral Annulation and Ring Opening of N-Aryloxyacetamides with 1-Alkynylcyclobutanols via Rhodium(III)-Catalyzed C-H/C-C Activations

A cascade [3 + 2] annulation and ring opening of N-aryloxyacetamides with 1-alkynylcyclobutanols via Rh(III)-catalyzed redox-neutral C-H/C-C activations using internal oxidative O-NHAc and -OH as the dual directing groups has been achieved. This reaction provided an efficient and regioselective approach to benzofuran derivatives with good functional group compatibility and high yields.

RhIII-Catalyzed Decarboxylative o-Acylation of Arenes Bearing an Oxidizing Directing Group

Here in we report, rhodium(III)-catalyzed decarboxylative acylation of arenes using α-oxocarboxylic acids as acyl surrogate. In this strategy, O–NHAc group act as an autocleavable oxidizing directing group (ODGauto), thus giving rise to ortho-acylated phenols in moderate to good yields. Mechanistic studies provided strong support for a kinetically relevant C–H bond activation. According to the best of our knowledge, this is the first report of Rhodium catalyzed decarboxylative acylation.

Rhodium(III)-catalysed cascade [3 + 2] annulation of: N -aryloxyacetamides with 3-(hetero)arylpropiolic acids: Synthesis of benzofuran-2(3 H)-ones

Herein, a cascade [3 + 2] annulation of N-aryloxyacetamides with 3-(hetero)arylpropiolic acids affording benzofuran-2(3H)-ones via rhodium(iii)-catalyzed redox-neutral C-H functionalization/isomerization/lactonization using an internal oxidative directing group O-NHAc was achieved. This catalytic system provides a regio- and stereoselective approach to synthesize (Z)-3-(amino(aryl)methylene)benzofuran-2(3H)-ones with exclusive Z configuration selectivity, acceptable yields and good functional group tolerance. Preliminary investigations on ultraviolet-visible and fluorescence behaviors reveal that the annulation products may be applied as a promising fluorescent probe for sensing metal cations, especially for cerium (Ce3+).

Rhodium(III)-Catalyzed Redox-Neutral Cascade [3 + 2] Annulation of N-Phenoxyacetamides with Propiolates via C-H Functionalization/Isomerization/Lactonization

A Rh(III)-catalyzed cascade [3 + 2] annulation of N-phenoxyacetamides with propiolates under mild conditions using the internal oxidative O-N bond as the directing group has been achieved. This catalytic system provides a regio- and stereoselective access to benzofuran-2(3H)-ones bearing exocyclic enamino motifs with exclusive Z configuration selectivity, acceptable to good yields and good functional group compatibility. Mechanistic investigations by experimental and density functional theory studies suggest that a consecutive process of C-H functionalization/isomerization/lactonization is likely to be involved in the reaction.

Rh(III)-Catalyzed Redox-Neutral Unsymmetrical C-H Alkylation and Amidation Reactions of N-Phenoxyacetamides

A Rh(III)-catalyzed unsymmetrical C-H alkylation and amidation of N-phenoxyacetamides with diazo compounds has been developed under mild and redox-neutral conditions, producing dinitrogen as the only byproduct. The reaction represents the first example of one-step, unsymmetrical difunctionalization of two ortho-C-H bonds. Experimental and computational studies support that N-phenoxyacetamides most likely undergo an initial ortho-C-H alkylation with diazo compounds via a Rh(III)-catalyzed C-H activation, and the resulting Rh(III) intermediate subsequently undergoes an intramolecular oxidative addition into the O-N bond to form a Rh(V) nitrenoid species that is protonated and further directed toward electrophilic addition to the second ortho position of the phenyl ring. This work might provide a new direction for unsymmetrical C-H difunctionalization reactions in an efficient manner.

Combination of Cp*RhIII-Catalyzed C?H Activation and a Wagner–Meerwein-Type Rearrangement

A combination of Cp*RhIII-catalyzed C?H activation and Wagner–Meerwein-type rearrangement was successfully achieved for the first time. Thus, bridged polycyclic molecules that are not readily accessible by other means were accessed under mild c

Rhodium(III)-Catalyzed Annulative Carbooxygenation of 1,1-Disubstituted Alkenes Triggered by C?H Activation

A Cp*RhIII-catalyzed annulative carbooxygenation of challenging 1,1-disubstituted alkenes triggered by C?H activation of N-aryloxyacetamides has been established, which affords 2,3-dihydrobenzofuran derivatives with a quaternary carbon center i

Cp?Rh(III)/Bicyclic Olefin Cocatalyzed C-H Bond Amidation by Intramolecular Amide Transfer

A bicyclic olefin was discovered as a cocatalyst in a Cp?Rh(III)-catalyzed C-H bond amidation proceeding by an intramolecular amide transfer in N-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh(III) intermediate to undergo oxidative addition into the O-N bond to form a Rh(V) nitrenoid species and subsequently direct the nitrenoid to add to the ortho position. The amide directing group plays a dual role as a cleavable coordinating moiety as well as an essential coupling partner for the C-H amidation. This methodology was successfully applied to the late-stage diversification of natural products and a marketed drug under mild conditions.

Rhodium(III)-Catalyzed ortho-Heteroarylation of Phenols through Internal Oxidative C-H Activation: Rapid Screening of Single-Molecular White-Light-Emitting Materials

Reported herein is the first example of a transition-metal-catalyzed internal oxidative C-H/C-H cross-coupling between two (hetero)arenes through a traceless oxidation directing strategy. Without the requirement of an external metal oxidant, a wide range of phenols, including phenol-containing natural products, can undergo the coupling with azoles to assemble a large library of highly functionalized 2-(2-hydroxyphenyl)azoles. The route provides an opportunity to rapidly screen white-light-emitting materials. As illustrative examples, two bis(triphenylamine)-bearing 2-(2-hydroxyphenyl)oxazoles, which are difficult to access otherwise, exhibit bright white-light emission, high quantum yield, and thermal stability. Also presented is the first example of the white-light emission, in a single excited-state intramolecular proton transfer system, of 2-(2-hydroxyphenyl)azoles, thus highlighting the charm of C-H activation in the discovery of new organic optoelectronic materials.