14738-27-3Relevant articles and documents
Scope and Mechanism of Iridium Porphyrin-Catalyzed S-H Insertion Reactions between Thiols and Diazo Esters
Dairo, Taiwo O.,Woo, L. Keith
, p. 927 - 934 (2017)
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.
Design, synthesis and biological evaluation of oxime lacking Psammaplin inspired chemical libraries as anti-cancer agents
Ali, Kasim,Chaturvedi, Priyank,Datta, Dipak,Kumar M, Srinivas Lavanya,Meena, Sanjeev,Panda, Gautam
, (2020/10/02)
In this study, we attempted the chemical simplification of Psammaplin (PsA), while retaining its activity in vitro. Inspired by the previous Structure Activity Relationship (SAR) studies on various PsA analogues and relying on the fact that oxime is metabolically unstable, we initially designed and synthesized a diverse library of PsA analogues and evaluated for cytotoxic activity. Among 32 compounds of Psammaplin analogues synthesized, the compound 10b was almost equally active as parent Psammaplin in vitro.
Catalyst-free, visible-light-promoted S-H insertion reaction between thiols and α-diazoesters
Chen, Shuwen,Huo, Congde,Liu, Cai,Ma, Ben,Song, Menghui,Wang, Ganggang,Yang, Jingya,Zhou, Hongyan
supporting information, p. 9494 - 9498 (2020/12/15)
A visible-light-promoted S-H insertion reaction between thiols and α-diazoesters was developed. The reaction proceeded smoothly at room temperature with a broad substrate scope, affording various thioethers in moderate to excellent yields. The catalyst- A
Radical-Mediated Strategies for the Functionalization of Alkenes with Diazo Compounds
Su, Yong-Liang,Liu, Geng-Xin,Liu, Jun-Wen,Tram, Linh,Qiu, Huang,Doyle, Michael P.
supporting information, p. 13846 - 13855 (2020/09/21)
One of the most common reactions of diazo compounds with alkenes is cyclopropanation, which occurs through metal carbene or free carbene intermediates. Alternative functionalization of alkenes with diazo compounds is limited, and a methodology for the addition of the elements of Z-CHR2 (with Z = H or heteroatom, and CHR2 originates from N2 CR2) across a carbon-carbon double bond has not been reported. Here we report a novel reaction of diazo compounds utilizing a radical-mediated addition strategy to achieve difunctionalization of diverse alkenes. Diazo compounds are transformed to carbon radicals with a photocatalyst or an iron catalyst through PCET processes. The carbon radical selectively adds to diverse alkenes, delivering new carbon radical species, and then forms products through hydroalkylation by thiol-assisted hydrogen atom transfer (HAT), or forms azidoalkylation products through an iron catalytic cycle. These two processes are highly complementary, proceed under mild reaction conditions, and show high functional group tolerance. Furthermore, both transformations are successfully performed on a gram-scale, and diverse γ-amino esters, γ-amino alcohols, and complex spirolactams are easily prepared with commercially available reagents. Mechanistic studies reveal the plausible pathways that link the two processes and explain the unique advantages of each.
