72410-77-6

Upstream product

• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 79-29-8 2,3-dimethylbutane 
• 22979-35-7 Methyl phenyldiazoacetate 
• 54502-24-8 copper(I) hexylacetylenide 
• 2039-49-8 3,5-diphehylisoxazole 
• 123-91-1 1,4-dioxane 
• 100-58-3 phenylmagnesium bromide 
• 931-53-3 Cyclohexyl isocyanide 
• 110-82-7 cyclohexane 
• 623-73-4 diazoacetic acid ethyl ester 
• 101-41-7 benzeneacetic acid methyl ester 
• 120-72-9 indole 

Relevant academic research and scientific papers

Transition metal-mediated reductive coupling of diazoesters

The first transition metal mediated reductive coupling of diazoesters through the terminal nitrogens is reported. The resulting tetrazene-bridged bis(diazenylacetate) serves as a novel dinucleating ligand to iron(III). DFT calculations suggest that the re

Blue LED-Mediated N-H Insertion of Indoles into Aryldiazoesters at Room Temperature in Batch and Flow: Reaction Kinetics, Density Functional Theory, and Mechanistic Study

Mild blue light-mediated N-H insertion of indole and its derivatives into aryldiazoesters has been reported in a batch and flow strategy to afford the corresponding N-alkylated product in moderate-to-excellent yield. Detailed high-performance liquid chromatography-based reaction kinetics measurements, control experiments, and kinetic isotope effect reveal that 3-substituted indoles with electron-withdrawing groups such as -CN and -CHO facilitated the product formation, whereas the electron-donating group retarded the process. The neutral indole performed in between them. Furthermore, Hammett plot and density functional theory-based transition-state optimization studies showed substantial correlation of the electronic nature of the substituents at the C3 position of indoles with the rate of the N-H insertion reaction. The strategy was utilized to synthesize a key intermediate for the natural product (-)-psychotrimine.

Photolytic amino etherification reactions of aryl diazoacetates with N-heterocycles and a stoichiometric amount of dioxane/tetrahydropyran in aqueous medium: Synthesis of 1,4-dioxepane/1,4,7-dioxazonan-6-one systems

Herein we have reported a blue LED mediated reaction of aryl diazoacetate with a stoichiometric amount of 1,4-dioxane/tetrahydropyran (THP) and various heterocycles like indoles, pyrroles, phthalimides, thiazolidinediones and hydantoins in water. During the reaction, various aryl diazoacetates were converted to oxonium ylides by reacting with 1,4-dioxane and THP. These ylides generated in aqueous medium (under metal- and base-free conditions) were then used for the amino etherification of the aforementioned heterocycles in excellent yield. The ylides underwent a [1,2] shift to afford substituted 1,4-dioxepanes. Phthalimide products were also converted to 1,4,7-dioxazonan-6-ones. Reaction kinetics, Hammett's plot and DFT calculations (solvent phase) rationalize the ylide formation and subsequent reactions with the nucleophiles. The reaction was also demonstrated at the multigram scale. This amino etherification reaction of aryl diazoacetates in aqueous medium demonstrated a sustainable process of converting toxic 1,4-dioxane in functionalizing heterocycles. This journal is

Grignard reagent dictated copper(I) phosphines catalyzed reductive coupling of diazo compounds: The chemistry beyond carbene generation

Copper-dppf catalyzed reductive coupling of diazo compounds through terminal nitrogen is reported. However, copper catalysts are known to produce carbene from diazo compounds; the reaction conditions played an important role in the formation of diazine over carbene generation. Several control experiments have been conducted to understand the reaction mechanism and found that the formation of a copper–Mg heterobimetallic complex would be responsible for the observed reactivity pattern. The reaction produced diazine as a reductive coupling product along with biphenyl as a by-product. All the synthesized diazines have been characterized fully by using analytical and spectroscopic techniques.

Ketenimine Formation Catalyzed by a High-Valent Cobalt Carbene in Bulky Alkoxide Ligand Environment

High-valent cobalt carbene Co(OR)2(CPh2) (OR = OCtBu2Ph) undergoes reaction with various isocyanides CNR (CNR = 2,6-dimethylphenyl isocyanide, 4-methoxyphenyl isocyanide, 2-chloro-6-methylphenyl isocyanide, adamantyl isocyanide) to yield the corresponding ketenimine. The reaction is accompanied by the formation of cobalt bis(alkoxide) bis(isocyanide) complexes Co(OR)2(CNR)2, which were independently synthesized and characterized. DFT calculations suggest the mechanism proceeds through isocyanide binding to Co, followed by intramolecular insertion into the Co-carbene bond to form the ketenimine. We have also conducted an investigation of the catalytic formation of ketenimines at room temperature using mixtures of diazoalkanes (diphenyldiazomethane, methyl diazo(phenyl)acetate, and ethyl diazoacetate) and isocyanides (2,6-dimethylphenyl isocyanide, 4-methoxyphenyl isocyanide, adamantyl isocyanide, cyclohexyl isocyanide, and benzyl isocyanide). While no catalytic reactivity was observed for diphenyldiazomethane, ester-substituted diazoalkanes (diazoesters) demonstrate catalytic turnover. Relatively high yields are observed for the reactions involving bulkier aliphatic substrates adamantyl and cyclohexyl isocyanides. Mechanistic studies suggest that the lack of catalytic reactivity involving diphenyldiazomethane results from the inability of Co(OR)2(CNR)2 to undergo carbene formation upon reaction with N2CPh2. In contrast, facile reaction is observed between Co(OR)2(CNR)2 and diazoesters, which enables the overall catalytic reactivity.

Isoxazolium N-ylides and 1-oxa-5-azahexa-1,3,5-trienes on the way from isoxazoles to 2H-1,3-oxazines

Theoretical and experimental studies of the reaction of isoxazoles with diazo compounds show that the formation of 2H-1,3- oxazines proceeds via the formation of (3Z)-1-oxa-5-azahexa-1,3,5-trienes which undergo a 6p-cyclization. The stationary points corresponding to the probable reaction intermediates, isoxazolium N-ylides, were located by DFT calculations at the B3LYP/6- 31G(d) level only for derivatives without a substituent in position 3 of the isoxazole ring. These isoxazolium N-ylides are thermodynamically and kinetically very unstable. According to the calculations and experimental results 2H-1,3-oxazines are usually more thermodynamically stable than the corresponding open-chain isomers, (3Z)-1-oxa-5-azahexa-1,3,5-trienes. The exception are oxaazahexatrienes derived from 5-alkoxyisoxazoles, which are thermodynamically more stable than the corresponding 2H-1,3- oxazines. Therefore, the reaction of diazo esters with 5-alkoxyisoxazoles is a good approach to 1,4-di(alkoxycarbonyl)-2- azabuta-1,3-dienes. The reaction conditions for the preparation of aryl- and halogen-substituted 2H-1,3-oxazines and 1,4-di(alkoxycarbonyl)- 2-azabuta-1,3-dienes from isoxazoles were investigated.

C-H insertion catalyzed by tetratolylporphyrinato methyliridium via a metal-carbene intermediate

C-H insertion reactions between different substrates and diazo reagents were catalyzed by tetratolylporphyrinato methyliridium (Ir(TTP)CH3). The highest yields were achieved for reactions between the bulky diazo reagent methyl 2-phenyldiazoacet

Copper-catalyzed synthesis of 2,4-disubstituted allenoates from α-diazoesters

Chemical equations presented. A Cu-catalyzed method for coupling α-substituted-α-diazoesters with terminal alkynes to give substituted allenoates is described. Key to the development of a selective method was the recognition that an adventitous base catalyzes the isomerization to form the allenoate product. A plausible mechanism is proposed, based in part on evidence against a mechanism that involves a Cu(I)-acetylide as a low-valent intermediate.

Catalytic Asymmetric C-H Activation of Alkanes and Tetrahydrofuran

Rhodium carbenoids derived from methyl aryldiazoacetates are capable of effective catalytic asymmetric C-H activation of a range of alkanes and tetrahydrofuran by a C-H insertion mechanism. Dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) (Rh2(S-DOSP)4) catalyzed decomposition of methyl aryldiazoacetates in the presence of alkanes results in intermolecular C-H insertions with good control of regioselectivity, diastereoselectivity, and enantioselectivity. The carbenoids derived from methyl aryldiazoacetates are considerably more chemoselective than carbenoids derived from diazoacetates. They strongly favor C-H insertions into secondary and tertiary sites. Formation of side products due to carbene dimerization is not a major problem with rhodium carbenoids derived from aryldiazoacetates.

Reactions of Azines. 12. Preparation and Reactions of Triphenylphosphonium Bromide

Preparation of triphenylphosphonium bromide (13), triphenylphosphonium iodide (15), and their corresponding ylides 14 and 16 was accomplished.The reaction of 14 with diphenylketene gave 2-methyl-4,9-diphenyl-9-(methoxycarbonyl)-4,9-dihydropyrazoloisoquinoline (19/20).The reaction of 16 with phenyl isocyanate gave 6,7-dimethyl-3-methoxy-1,3-diphenyl-1H-imidazopyrazol-2(3H)-one (27b), 2,3-dimethyl-9-(methoxycarbonyl)-9-phenyl-4,9-dihydropyrazoloquinazoline (30), and 2,3-dimethyl-9-phenylpyrazoloquinazoline (31).Phenylacetoxyketene, on reacting with triphenylphosphorane (35), gave 2-methyl-4,9-diphenylpyrazoloisoquinoline (40).Carbon disulfide with ylide 16 gave the 2,3-dimethyl-9-(methoxycarbonyl)-9H-pyrazolobenzothiazine (45) and desaurine (42) as well as the trans-5,10-bis(methoxycarbonyl)-5,10-diphenyldipyrazolodiazadithiocine (46).Confirmation of the structures 31, 42, and 46 was obtained by crystallographic analyses.