128080-16-0

Upstream product

• 99768-12-4 4-methoxycarbonylphenylboronic acid 
• 99-76-3 methyl 4-hydroxylbenzoate 

Downstream Products

• 1159180-80-9 C₂₆H₃₁N₃O₈ 
• 1159180-79-6 C₂₆H₃₁N₃O₉ 

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.

An internal oxidant-directing strategy enabling transition metal-free C–S bond ligation

Organic sulfur compounds have broad applications in biology, medicine and material sciences and intensive efforts have been devoted to developing mild and general C–S bond-forming methods. However, a mild, transition-metal-free, direct C–H bond functionalization method remains elusive. Here, we report the use of an internal oxidant-directing strategy to achieve this goal. The cascade reactions described here show excellent chemoselectivity and a wide substrate scope for both oxyamines and sulfenylation reagents. This study enlarges the synthesis toolbox for preparing structurally diverse sulfilimines under mild conditions.

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.

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.

Rhodium(III)-Catalyzed Cascade Redox-Neutral C–H Functionalization and Aromatization: Synthesis of Unsymmetrical ortho-Biphenols

An efficient rhodium(III)-catalyzed coupling reaction of N-aryloxyacetamides with 6-diazo-2-cyclohexenones through a cascade redox-neutral C–H functionalization and aromatization has been developed. This novel and scalable transformation provides a straightforward way to construct unsymmetrical ortho-biphenols with broad substrate scope under mild and redox-neutral conditions. The synthetic utility of this approach is demonstrated in the late-stage functionalization of bioactive compounds and the synthesis of an optically active ortho-biphenol. (Figure presented.).

Acylation of Csp2-H bond with acyl sources derived from alkynes: Rh-Cu bimetallic catalyzed CC bond cleavage

A Rh-Cu bimetallic catalyzed o-acylation of acyloxacetamide with alkynes has been described. This transformation provides a novel, concise way to synthesize ortho-acylphenols using functionalized alkynes as acylating reagents. Mechanistic studies revealed a Rh-Cu relay process, in which O2 plays a critical role for the formation of carbonyl compounds.

Rh(iii)-catalyzed and alcohol-involved carbenoid C-H insertion into N-phenoxyacetamides using α-diazomalonates

Here we report a new and mild Rh(iii)-catalyzed and alcohol-involved carbenoid C-H insertion into N-phenoxyacetamides using α-diazomalonates. This reaction provided a straightforward way for installing both an α-quaternary carbon center and a free-OH moiety into the phenyl ring, thus giving access to useful 2-(2-hydroxyphenyl)-2-alkoxymalonates with good substrate/functional group tolerance. This journal is

Rhodium(iii)-catalyzed C-H activation/[4+3] annulation of N-phenoxyacetamides and α,β-unsaturated aldehydes: An efficient route to 1,2-oxazepines at room temperature

An efficient Rh(iii)-catalyzed coupling reaction of N-phenoxyacetamides with α,β-unsaturated aldehydes to give 1,2-oxazepines via C-H activation/[4+3] annulation has been developed. This transformation does not require oxidants and features C-C/C-N bond formation to yield seven-membered oxazepine rings at room temperature. Further derivation of 1,2-oxazepines leads to important chroman derivatives. This journal is