Organocatalytic asymmetric nitroso aldol reaction of α-substituted malonamates

• Ekta Gupta,
• Narendra Kumar Vaishanv,
• Sandeep Kumar,
• Raja Krishnan Purshottam,
• Ruchir Kant and
• Kishor Mohanan

Beilstein J. Org. Chem. 2022, 18, 217–224, doi:10.3762/bjoc.18.25

• ). The disubstituted malonamates underwent facile oxyamination, and the products were obtained in excellent yields and enantioselectivities (4k, 4l). Of note, the reaction was also feasible with heterocyclic malonamate, albeit with moderate yield and enantioselectivity (4m). Aliphatic malonamate was also

Synthesis of 3-substituted isoxazolidin-4-ols using hydroboration–oxidation reactions of 4,5-unsubstituted 2,3-dihydroisoxazoles

• Lívia Dikošová,
• Júlia Laceková,
• Ondrej Záborský and
• Róbert Fischer

Beilstein J. Org. Chem. 2020, 16, 1313–1319, doi:10.3762/bjoc.16.112

• substitution reactions of properly substituted hydroxylamines [19][20] and N-hydroxyphthalimides [21][22][23][24] as well as by Tamao oxidations of 4-silylisoxazolidines [25][26]. Very recently, Tomkinson et al. described a simple and effective method for an intramolecular oxyamination of allylic N-tosyl

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• 2009, Jang’s group disclosed the first example of the anodic oxidation of enamines (SOMO protocol) in terms of asymmetric α-oxyamination of aldehydes [74]. Galvanostatic electrolysis of aldehydes 105 in a single compartment cell using TEMPO (106) in presence of chiral secondary amine catalyst 107

Tandem copper and photoredox catalysis in photocatalytic alkene difunctionalization reactions

• Nicholas L. Reed,
• Madeline I. Herman,
• Vladimir P. Miltchev and
• Tehshik P. Yoon

Beilstein J. Org. Chem. 2019, 15, 351–356, doi:10.3762/bjoc.15.30

• describe a method for alkene oxyamination and diamination that utilizes simple carbamate and urea groups as nucleophilic heteroatom donors. This method uses a tandem copper–photoredox catalyst system that is operationally convenient. The identity of the terminal oxidant is critical in these studies. Ag(I

• ) salts proved to be unique in their ability to turn over the copper cocatalyst without deleteriously impacting the reactivity of the organoradical intermediates. Keywords: copper; diamination; oxidative functionalization; oxyamination; photoredox catalysis; radical; Introduction Over the past decade, a

• combines the photoredox activation of electron-rich alkenes with copper(II)-mediated oxidation of electron-rich radicals as described by Kochi [18][19][20]. These studies resulted in the development of a general new protocol for oxyamination (Figure 1a) and diamination (Figure 1b) of alkenes. The mechanism

A survey of chiral hypervalent iodine reagents in asymmetric synthesis

• Soumen Ghosh,
• Suman Pradhan and
• Indranil Chatterjee

Beilstein J. Org. Chem. 2018, 14, 1244–1262, doi:10.3762/bjoc.14.107

• formation and ring opening of aziridinium intermediate 58 elucidate the product formation in this transformation [51]. Wirth et al. successfully employed I(III) reagent 8b in combination with trimethylsilyltriflate (TMSOTf) for the stereoselective oxyamination of 59 to furnish isourea 60 with >99% ee

• diamination of alkenes. Stereoselective oxyamination of alkenes reported by Wirth et al. Enantioselective and regioselective aminofluorination by Nevado et al. Fluorinated difunctionalization reported by Jacobsen et al. Aryl rearrangement reported by Wirth et al. α-Arylation of β-ketoesters. Asymmetric α

Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

• Brett N. Hemric and
• Qiu Wang

Beilstein J. Org. Chem. 2016, 12, 22–28, doi:10.3762/bjoc.12.4

• Brett N. Hemric Qiu Wang Department of Chemistry, Duke University, Durham, NC, USA 10.3762/bjoc.12.4 Abstract This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O

• . Keywords: copper; electrophilic amination; olefin oxyamination; Introduction The 1,2-oxyamino motif is highly valuable and found in a vast range of biologically active natural products, pharmaceuticals, and agrochemicals (Figure 1) [1][2]. Representative examples include salmeterol (Advair®), a β2

• class of molecules is highly valued. Toward this end, intermolecular olefin oxyamination allows for direct and modular installation of both oxygen and amino groups to readily available olefins in a single step, representing a powerful and appealing approach over multistep sequences [7][8][9]. Sharpless

Enantioselective total synthesis of (R)-(−)-complanine

• Krystal A. D. Kamanos and
• Jonathan M. Withey

Beilstein J. Org. Chem. 2012, 8, 1695–1699, doi:10.3762/bjoc.8.192

• complanata, and known to be a causative agent in inflammation. An organocatalytic, asymmetric oxyamination of a homoconjugated all-Z-dienal intermediate provides versatile and efficient access to the natural product. Keywords: complanine; enantioselective synthesis; marine fireworm; nitrosoaldol

Asymmetric one-pot sequential Friedel–Crafts-type alkylation and α-oxyamination catalyzed by a peptide and an enzyme

• Kengo Akagawa,
• Ryota Umezawa and
• Kazuaki Kudo

Beilstein J. Org. Chem. 2012, 8, 1333–1337, doi:10.3762/bjoc.8.152

• –Crafts-type alkylation of α,β-unsaturated aldehydes followed by an α-oxyamination was realized. The reaction in aqueous solvent to promote the enzymatic oxidation, and the use of a peptide catalyst compatible with such conditions, were essential. The present sequential reaction afforded oxygen

• -functionalized indole or pyrrole derivatives in a highly enantioselective manner. Keywords: Friedel–Crafts-type alkylation; laccase; one-pot reaction; organocatalysis; α-oxyamination; resin-supported peptide catalyst; Findings Indole derivatives represent a class of biologically active compounds [1][2][3], and

• FCAA reaction toward α,β-unsaturated aldehydes through iminium intermediates [32][37], and an asymmetric α-oxyamination of aldehydes via enamines [33], they are expected to be suitable for a one-pot sequential reaction to make the chiral indoles mentioned above. Herein, we report on an enantioselective