277754-35-5

Upstream product

• 1165952-92-0 cyclohexa-1,4-diene 
• 22979-35-7 Methyl phenyldiazoacetate 

Downstream Products

• 3469-00-9 methyl 2,2-diphenylacetate 
• 13027-73-1 methyl 2-cyclohexyl-2-phenylacetate 

Relevant academic research and scientific papers

Blue light-promoted photolysis of aryldiazoacetates

Aryldiazoacetates can undergo photolysis under blue light irradiation (460-490 nm) at room temperature and under air in the presence of numerous trapping agents, such as styrene, carboxylic acids, amines, alkanes and arenes, thus providing a straighforward and general platform for their mild functionalization.

Elevated catalytic activity of ruthenium(II)-porphyrin-catalyzed carbene/nitrene transfer and insertion reactions with n-heterocyclic carbene ligands

Bis(NHC)ruthenium(II)-porphyrin complexes were designed, synthesized, and characterized. Owing to the strong donor strength of axial NHC ligands in stabilizing the trans Mi￡CRR′/Mi￡NR moiety, these complexes showed unprecedently high catalytic activity towards alkene cyclopropanation, carbene C-H, N-H, S-H, and O-H insertion, alkene aziridination, and nitrene C-H insertion with turnover frequencies up to 1950 min-1. The use of chiral [Ru(D4-Por)(BIMe)2] (1 g) as a catalyst led to highly enantioselective carbene/nitrene transfer and insertion reactions with up to 98 % ee. Carbene modification of the N terminus of peptides at 37 °C was possible. DFT calculations revealed that the trans axial NHC ligand facilitates the decomposition of diazo compounds by stabilizing the metal-carbene reaction intermediate.

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

Ruthenium Catalysts and Uses Thereof

Ruthenium nanoparticles supported on non-cross-linked soluble polystyrene were prepared by reacting [RuCl2(C6H5CO2Et)]2 with polystyrene in open air. They effectively catalyze intra- and intermolecular carbenoid insertion into C—H and N—H bonds, alkene cyclopropanation, and ammonium ylide/[2,3]-sigmatropic rearrangement reactions. This supported ruthenium catalyst is much more reactive than [RuCl2(p-cymene)]2 and Ru(Por)CO] for catalytic intermolecular carbenoid C—H bond insertion into saturated alkanes. By using a-diazoacetamide as a substrate for intramolecular carbenoid C—H insertion, the supported ruthenium catalyst can be to recovered and reused for ten successive iterations without significant loss of activity.

Combined experimental and computational studies of heterobimetallic Bi-Rh paddlewheel carboxylates as catalysts for metal carbenoid transformations

(Chemical Equation Presented) The catalytic activity of heterobimetallic Bi-Rh paddlewheel carboxylate complexes has been evaluated for the first time in the context of metal carbenoid chemistry. The Bi-Rh carboxylate complexes were found to effectively catalyze both cyclopropanation reactions and C-H insertions as well as reactions involving ylide intermediates with similar selectivity profiles to analogous dirhodium complexes. The heterometallic complex BiRh(O2CCF3)3(O2CCH3) was found to be approximately 1600 times less reactive than its homometallic analogue Rh2(O2CCF3)3(O 2CCH3) toward the decomposition of methyl phenyldiazoacetate. The observed difference in reactivity is in good agreement with a computational model system where axial coordination to the second rhodium active site is considered for the dirhodium catalyst.

Rhodium chemzymes: Michaelis-Menten kinetics in dirhodium(II) carboxylate-catalyzed carbenoid reactions

Rhodium carboxylate-mediated reactions of diazoketones involving cyclopropanation, C-H insertion, and aromatic C-C double bond addition/electrocyclic ring opening obey saturation (Michaelis-Menten) kinetics. Axial ligands for rhodium, including aromatic hydrocarbons and Lewis bases such as nitriles, ethers, and ketones, inhibit these reactions by a mixed kinetic inhibition mechanism, meaning that they can bind both to the free catalyst and to the catalyst - substrate complex. Substrate inhibition can also be exhibited by diazocompounds bearing these groupings in addition to the diazo group. The analysis of inhibition shows that the active catalyst uses only one of its two coordination sites at a time for catalysis. Some ketones exhibit the interesting property that they selectively bind to the catalyst - substrate complex. The similarity of the kinetic constants from different types of reactions with similar diazoketones, regardless of the linking unit or the environment of the reacting alkene, suggests that the rate-determining step is the generation of the rhodium carbenoid. A very useful rhodium carboxylate catalyst for asymmetric synthesis, Rh2(DOSP)4, shows slightly slower kinetic parameters than the achiral catalysts, implying that enantiose-lectivity of this catalyst is based on slowing reactions from one of the enantiotopic faces of the reactant, rather than any type of ligand-accelerated catalysis. A series of rhodium catalysts derived from acids with pKas spanning 4 orders of magnitude give very similar kinetic constants.

Conformational analysis and stereochemical assignments of products derived from C-H activation at secondary sites

The products derived from C-H activation of secondary sites by rhodium-carbenoids exist in a well-defined conformation. Consequently, their stereochemical assignment can be readily determined on the basis of chemical shift arguments.

Intermolecular cyclopropanation versus CH insertion in Rh(II)-catalyzed carbenoid reactions

The product ratio of intermolecular insertion and cyclopropanation in transition metal-catalyzed diazo decompositions depends strongly upon the metal, its ligands and upon the substituents of the diazo compound. Ethyl diazoacetate (2a) reacts with cyclohexene (1) almost exclusively by cyclopropanation. However, diazomalonate (2d) and methyl 2-diazophenylacetate (2e) in the presence of Rh(II) catalysts exhibit a marked tendency towards allylic CH insertion. With 1,4-cyclohexadiene (6), methyl 2- diazophenylacetate (2e) in the presence of chiral Rh(II) catalysts affords the allylic insertion product 7 in almost quantitative yield and with up to 74% ee. (C) 2000 Elsevier Science Ltd.