Oxidative hydrolysis of aliphatic bromoalkenes: scope study and reactivity insights

• Amol P. Jadhav and
• Claude Y. Legault

Beilstein J. Org. Chem. 2024, 20, 1286–1291, doi:10.3762/bjoc.20.111

• Amol P. Jadhav Claude Y. Legault Department of Chemistry, Centre in Green Chemistry and Catalysis, Université de Sherbrooke, Québec J1K 2R1, Canada 10.3762/bjoc.20.111 Abstract We have developed an operationally simple method for the synthesis of dialkyl α-bromoketones from bromoalkenes by

• utilizing a hypervalent iodine-catalyzed oxidative hydrolysis reaction. This catalytic process provides both symmetrical and unsymmetrical dialkyl bromoketones with moderate yields across a broad range of bromoalkene substrates. Our studies also reveal the formation of Ritter-type side products by an

• alternative reaction pathway. Keywords: bromoalkenes; bromoketones; hypervalent iodine; oxidative hydrolysis; Ritter-type; Introduction Organic synthesis heavily relies on oxidative transformations to facilitate chemical reactions. One popular method for achieving these transformations is using redox-active

Decarboxylative 1,3-dipolar cycloaddition of amino acids for the synthesis of heterocyclic compounds

• Xiaofeng Zhang,
• Xiaoming Ma and
• Wei Zhang

Beilstein J. Org. Chem. 2023, 19, 1677–1693, doi:10.3762/bjoc.19.123

• could also be applied for the synthesis of pyrrolobenzodiazepines when using 2-bromoketones instead of the acid chlorides affording products 24a–g in 59–77% yields with 3:1 to 6:1 dr (Scheme 15). The pyrroloquinazolines and pyrrolobenzodiazepines made by this route have structure similarity with

Eschenmoser coupling reactions starting from primary thioamides. When do they work and when not?

• Lukáš Marek,
• Jiří Váňa,
• Jan Svoboda and
• Jiří Hanusek

Beilstein J. Org. Chem. 2023, 19, 808–819, doi:10.3762/bjoc.19.61

• water) tend to the formation [5][6] of the ECR product (XIV). A similar tendency to produce either ECR or thiazole products depending on the solvent was observed already by Eschenmoser and his co-workers for the reaction of α-bromoketones with thiolactams [23]. On the other hand, Bergman et al

Electrochemical vicinal oxyazidation of α-arylvinyl acetates

• Yi-Lun Li,
• Zhaojiang Shi,
• Tao Shen and
• Ke-Yin Ye

Beilstein J. Org. Chem. 2022, 18, 1026–1031, doi:10.3762/bjoc.18.103

• development of a green, efficient, and sustainable protocol for the synthesis of azidoketones is of great significance [7][8][9]. Retrosynthetically, the nucleophilic substitution of α-bromoketones by sodium azide [10] and oxidation of the azido alcohols [11] are among the most straightforward methods to

Mechanochemical halogenation of unsymmetrically substituted azobenzenes

• Dajana Barišić,
• Mario Pajić,
• Ivan Halasz,
• Darko Babić and
• Manda Ćurić

Beilstein J. Org. Chem. 2022, 18, 680–687, doi:10.3762/bjoc.18.69

• -halosuccinimide (NXS, X = Br, I) as halogen source [47]. Two years later in 2017, Eslami's group applied a ball-milling method to synthesize aryl bromides and α-bromoketones with N-bromosuccinimide (NBS) and MCM-41-SO3H catalyst and no liquid additives [48]. In 2018, Wang and co-workers developed the ball-milling

Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

• Zhonglie Yang,
• Yutong Liu,
• Kun Cao,
• Xiaobin Zhang,
• Hezhong Jiang and
• Jiahong Li

Beilstein J. Org. Chem. 2021, 17, 771–799, doi:10.3762/bjoc.17.67

• irradiation (Scheme 61). It was worth mentioning that longer reaction times and increased DIPEA loading were required owing to the inactivity of α-bromoketones, esters, and nonactivated sulfones; however, corresponding products could be given in high yield. When the DIPEA molarity was double that of

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

•  18b) [65]. Jiang et al. also reported a series of radical coupling reactions using different CPAs 135a–g and DPZ, with the first examples using α-bromoketones 136 and α-amino acids 137 as radical precursors (Scheme 19a) [66]. The proposed mechanism proceeds through a reductive quenching cycle to

Copper-based fluorinated reagents for the synthesis of CF₂R-containing molecules (R ≠ F)

• Louise Ruyet and
• Tatiana Besset

Beilstein J. Org. Chem. 2020, 16, 1051–1065, doi:10.3762/bjoc.16.92

• the SCF2PO(OEt)2 derivatives [53]. In the same vein, the reaction of the CuCF2PO(OEt)2 species, generated from CuSCN, with α-bromoketones provided the α-SCF2PO(OEt)2-containing ketones [54] (Scheme 10). In 2019, the group of Goossen developed an approach to access SCF2PO(OEt)2-containing arenes based

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• (Scheme 18). Rather recently, Liu and co-workers [62] reported an alternative approach to the synthesis of 3-brominated indolizines via copper-catalyzed three-component cascade reactions of pyridines 56, α-bromoketones 57 and maleic anhydride (58). The construction of the products involved in the three

A new and convenient synthetic way to 2-substituted thieno[2,3-b]indoles

• Roman A. Irgashev,
• Arseny A. Karmatsky,
• Gennady L. Rusinov and
• Valery N. Charushin

Beilstein J. Org. Chem. 2015, 11, 1000–1007, doi:10.3762/bjoc.11.112

• cyclization of 3-(2-nirtophenyl)thiophenes 5 via nitrene intermediates [25][26], and condensation of 3-unsubstituted indolin-2-thione 6 with aliphatic α-bromoaldehydes, α-bromoketones [27] or 3-halochromones (Hlg = Cl, Br) [28] under basic conditions (Scheme 1). However, all synthetic methods mentioned above

The Eschenmoser coupling reaction under continuous-flow conditions

• Sukhdeep Singh,
• J. Michael Köhler,
• Andreas Schober and
• G. Alexander Groß

Beilstein J. Org. Chem. 2011, 7, 1164–1172, doi:10.3762/bjoc.7.135

• is quite a valuable, metal free, carbon–carbon bond forming reaction. The necessary starting materials of type 3 can be prepared by S-alkylation of secondary thioamide or thiolactame building blocks of type 2 with α-bromoketones 1 (X = Br). The carbon–carbon coupling occurs between these building

• type 5 undergo the S-alkylation with α-bromoketones more readily than ternary thioamides. However, the specific reactivity of both reaction steps obviously depends on the building blocks used and their specific reactivity. For the present work we chose only commercially available α-bromoketone building

• bromoketones because of their known good reactivity and selectivity for the sulfide contraction [1]. Recently, we investigated the reaction of dihydropyrimidine derivatives of type 11 with different aliphatic ketones 10 under batch conditions. In that case the S-alkylated substrates 12 did not undergo the

Reduction of arenediazonium salts by tetrakis(dimethylamino)ethylene (TDAE): Efficient formation of products derived from aryl radicals

• Mohan Mahesh,
• John A. Murphy,
• Franck LeStrat and
• Hans Peter Wessel

Beilstein J. Org. Chem. 2009, 5, No. 1, doi:10.3762/bjoc.5.1

• (bromomethyl)arenes [48], mono and trichloromethyl azaheterocycles [49][50], 2-(dibromomethyl)quinoxaline [51], α-bromoketones [52] have been reported. Vanelle and co-workers recently reported a photoinduced reduction of p-nitrobenzaldehyde in the presence of TDAE [53]. The utility of TDAE as a strong electron