On the cause of low thermal stability of ethyl halodiazoacetates

• Magnus Mortén,
• Martin Hennum and
• Tore Bonge-Hansen

Beilstein J. Org. Chem. 2016, 12, 1590–1597, doi:10.3762/bjoc.12.155

• organic chemists ever since Theodor Curtius synthesized ethyl diazoacetate (EDA, 1) for the first time in 1883 [1]. Even today, after more than a century of research, diazo compounds still play an important role in state-of-the-art organic chemistry in areas such as for example C–H functionalization [2

• diazoacetate (EDA) is relatively safe to handle, being thermally stable at room temperature with a reported half-life of 109 hours at 100 °C [3]. EDA is also stable in weakly acidic solutions such as glacial acid [4], but reactive in the presence of Lewis acids, a key property for its effectiveness in

• relative to their aliphatic counterparts is explained by the electron-acceptor character of the carbonyl group. The presence of one or two ester groups α to the diazo functionality leads to increased stability so that elevated temperatures are usually needed in order to induce thermal decomposition. Ethyl

Synthesis of quinoline-3-carboxylates by a Rh(II)-catalyzed cyclopropanation-ring expansion reaction of indoles with halodiazoacetates

• Magnus Mortén,
• Martin Hennum and
• Tore Bonge-Hansen

Beilstein J. Org. Chem. 2015, 11, 1944–1949, doi:10.3762/bjoc.11.210

• rapidly (<1min reaction time) from ethyl diazoacetate (EDA), DBU and an N-halo succinimide (NXS) of choice according to Scheme 1. In this letter we report our results from the reactions between a series of indoles with halodiazoacetates. Results and Discussion We initiated our study by investigating the

Ethyl diazoacetate synthesis in flow

• Mariëlle M. E. Delville,
• Jan C. M. van Hest and
• Floris P. J. T. Rutjes

Beilstein J. Org. Chem. 2013, 9, 1813–1818, doi:10.3762/bjoc.9.211

• conditions, a production yield of 20 g EDA day−1 was achieved using a microreactor with an internal volume of 100 μL. Straightforward scale-up or scale-out of microreactor technology renders this method viable for industrial application. Keywords: diazo compounds; diazotization; ethyl diazoacetate (EDA

α-Bromodiazoacetamides – a new class of diazo compounds for catalyst-free, ambient temperature intramolecular C–H insertion reactions

• Åsmund Kaupang and
• Tore Bonge-Hansen

Beilstein J. Org. Chem. 2013, 9, 1407–1413, doi:10.3762/bjoc.9.157

• ][27][28][29][30], as well as carbon, e.g., in aldol reactions with aldehydes [31][32], ketones [33][34] and imines [35][36]. The first syntheses of α-halodiazoacetic esters, reported in the late 1960s, employed electrophilic diazoalkane substitution; the mercury or silver salts of ethyl diazoacetate

• (EDA) were reacted with sources of electrophilic halogen (SO2Cl2, Br2 or I2). These protocols allowed Gerhart and Schöllkopf et al. to study the properties of the resulting α-halodiazoacetates and the reactivity of their photolytically derived carbenes [26][27][28][29][30]. Some ten years later, Regitz

Gold-catalyzed naphthalene functionalization

• Pedro J. Pérez,
• M. Mar Díaz-Requejo and
• Iván Rivilla

Beilstein J. Org. Chem. 2011, 7, 653–657, doi:10.3762/bjoc.7.77

• unsaturated substrates, including aromatics [3]. Thus, the reaction of ethyl diazoacetate (EDA) with benzene in the presence of such catalysts at room temperature exclusively affords the cycloheptatriene product in quantitative yields. The reaction, always referred to the intermolecular version, was later

Sequential Au(I)-catalyzed reaction of water with o-acetylenyl-substituted phenyldiazoacetates

• Lei Zhou,
• Yizhou Liu,
• Yan Zhang and
• Jianbo Wang

Beilstein J. Org. Chem. 2011, 7, 631–637, doi:10.3762/bjoc.7.74

• , Díaz-Requejo, Nolan, Pérez and co-workers reported the first example of carbene transfer from ethyl diazoacetate (EDA) using (IPr)AuCl. The subsequent generation of a gold carbene was followed by insertion into a phenyl C–H bond, an O–H bond, or an N–H bond [6]. Similar reactions were also reported by