33767-33-8

Upstream product

• 4143-61-7 diethyl diazodicarboxylate 
• 22979-35-7 Methyl phenyldiazoacetate 
• 100-53-8 phenylmethanethiol 

Downstream Products

• 1011458-36-8 ethyl 2-(benzylthio)-2-[(o-methoxycarbonylmethyl)phenyl]acetate 

Relevant academic research and scientific papers

Rhodium-catalyzed reaction of diazoacetates, thiols and azodicarboxylates: An unusual 1,2-aza shift from a sulfonium ylide

A one-pot reaction of diazoacetates, thiols and azodicarboxylates in the presence of a dirhodium acetate catalyst gave N,S-ketals in good yields. This reaction proceeded via an unusual 1,2-aza shift from a sulfonium ylide intermediate. Georg Thieme Verlag

FeII-catalysed insertion reaction of α-diazocarbonyls into X-H bonds (X = Si, S, N, and O) in dimethyl carbonate as a suitable solvent alternative

The insertion reaction of a broad range of diazo compounds into Si-H bonds was found to be efficiently catalysed by Fe(OTf)2 in an emerging green solvent i.e. dimethyl carbonate (DMC). The α-silylated products were obtained in good to excellent yields (up to 95%). Kinetic studies showed that the extrusion of N2 to form an iron carbene intermediate is rate-limiting. The iron-catalysed insertion reaction of methyl α-phenyl-α-diazoacetate into polar X-H bonds (S-H, N-H, and O-H) was also established in DMC.

Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds

An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).

Scope and Mechanism of Iridium Porphyrin-Catalyzed S-H Insertion Reactions between Thiols and Diazo Esters

The insertion of carbenes derived from ethyl diazoacetate (EDA), methyl diazoacetate (MDA), methyl phenyldiazoacetate (MPDA), and methyl (p-tolyl)diazoacetate (MTDA) into the S-H bonds of aromatic and aliphatic thiols was catalyzed by (5,10,15,20-tetratolylporphyrinato)methyliridium(III), Ir(TTP)CH3, at ambient temperatures. Yields of the resulting thioether products were as high as 97% for aromatic thiols, with catalyst loadings as low as 0.07 mol %. Thiol binding to Ir(TTP)CH3 was measured at 23 °C by titration studies, providing equilibrium constants, Kb, ranging from 4.25 × 102 to 1.69 × 103 and increasing in the order p-nitrobenzenethiol a mechanism that involves a rate-limiting nucleophilic attack of thiols on an iridium-carbene species, where the major species present in the reaction solution is an inactive, hexacoordinate Ir-thiol complex.

Highly enantioselective S-H bond insertion cooperatively catalyzed by dirhodium complexes and chiral spiro phosphoric acids

The first highly enantioselective S-H bond insertion reaction was developed by cooperative catalysis of dirhodium(ii) carboxylates and chiral spiro phosphoric acids (SPAs) under mild and neutral reaction conditions with fast reaction rates, high yields (77-97% yields), and excellent enantioselectivities (up to 98% ee). The catalytic S-H bond insertion reaction provides a highly efficient method for the synthesis of chiral sulfur-containing compounds and advances the synthesis of a chiral sulfur-containing drug (S)-Eflucimibe. A systematic 31P NMR study revealed that no ligand exchange between dirhodium(ii) carboxylates and SPAs occurred in the reaction. The distinct behaviors of cooperative catalysts Rh2(TPA)4/(R)-1a and the prepared complex Rh2(R-1a)4 observed by in situ FT-IR spectroscopy excluded the feasibility of Rh2(R-SPA)4 being the real catalyst. DFT calculations showed that the activation barrier in the proton shift step became remarkably low as promoted by SPAs. Based on the experimental results and the calculations, the SPA was proposed as a chiral proton shuttle for the proton shift in reaction. Additionally, the single crystal structures of several SPAs were measured and used to rationalize the configurations of the S-H insertion products obtained in the reactions. The rigid and crowded environment around the SPAs ensures the high enantioselectivity in the S-H bond insertion reaction.