25393-66-2

Upstream product

• 21384-41-8 N-benzoyl-2-methylaziridine 
• 6168-72-5 2-Amino-1-propanol 
• 100-47-0 benzonitrile 
• 100-52-7 benzaldehyde 
• 24629-34-3 N-(1-hydroxypropan-2-yl)benzamide 
• 78007-50-8 N-(prop-1-en-2-yl)benzamide 
• 4380-77-2 O-phenylbenzohydroxamic acid 
• 2446-51-7 N-methoxybenzamide 
• 185197-16-4 2-propenyl (Z)-N-methoxybenzimidate 
• 41071-35-6 (Z)-N-methoxybenzenecarboximidoyl chloride 
• 35590-17-1 propyl benzenecarboximidoate 
• 591-50-4 iodobenzene 
• 119072-55-8 tert-butylisonitrile 
• 98-88-4 benzoyl chloride 

Downstream Products

• 125558-95-4 4,5-dihydro-4-methyl-2-phenyl-1,3-oxazin-6-one 

Relevant academic research and scientific papers

σ-Bond Hydroboration of Cyclopropanes

Hydroboration of alkenes is a classical reaction in organic synthesis in which alkenes react with boranes to give alkylboranes with subsequent oxidation resulting in alcohols. The double bond (π-bond) of alkenes can be readily reacted with boranes owing to its high reactivity. However, the single bond (σ-bond) of alkanes has never been reacted. To pursue the development of σ-bond cleavage, we selected cyclopropanes as model substrates since they present a relatively weak σ-bond. Herein, we describe an iridium-catalyzed hydroboration of cyclopropanes, resulting in β-methyl alkylboronates. These unusually branched boronates can be derivatized by oxidation or cross-coupling chemistry, accessing "designer"products that are desired by practitioners of natural product synthesis and medicinal chemistry. Furthermore, mechanistic investigations and theoretical studies revealed the enabling role of the catalyst.

Site-Specific C(sp3)–H Aminations of Imidates and Amidines Enabled by Covalently Tethered Distonic Radical Anions

The utilization of N-centered radicals to synthesize nitrogen-containing compounds has attracted considerable attention recently, due to their powerful reactivities and the concomitant construction of C?N bonds. However, the generation and control of N-centered radicals remain particularly challenging. We report a tethering strategy using SOMO-HOMO-converted distonic radical anions for the site-specific aminations of imidates and amidines with aid of the non-covalent interaction. This reaction features a remarkably broad substrate scope and also enables the late-stage functionalization of bioactive molecules. Furthermore, the reaction mechanism is thoroughly investigated through kinetic studies, Raman spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations, revealing that the aminations likely involve direct homolytic cleavage of N?H bonds and subsequently controllable 1,5 or 1,6 hydrogen atom transfer.

Catalytic Alkene Difunctionalization via Imidate Radicals

The first catalytic strategy to harness imidate radicals has been developed. This approach enables alkene difunctionalization of allyl alcohols by photocatalytic reduction of their oxime imidates. The ensuing imidate radicals undergo consecutive intra- and intermolecular reactions to afford (i) hydroamination, (ii) aminoalkylation, or (iii) aminoarylation, via three distinct radical mechanisms. The broad scope and utility of this catalytic method for imidate radical reactivity is presented, along with comparisons to other N-centered radicals and complementary, closed-shell imidate pathways.

Directed β C-H Amination of Alcohols via Radical Relay Chaperones

A radical-mediated strategy for β C-H amination of alcohols has been developed. This approach employs a radical relay chaperone, which serves as a traceless director that facilitates selective C-H functionalization via 1,5-hydrogen atom transfer (HAT) and enables net incorporation of ammonia at the β carbon of alcohols. The chaperones presented herein enable direct access to imidate radicals, allowing their first use for H atom abstraction. A streamlined protocol enables rapid conversion of alcohols to their β-amino analogs (via in situ conversion of alcohols to imidates, directed C-H amination, and hydrolysis to NH2). Mechanistic experiments indicate HAT is rate-limiting, whereas intramolecular amination is product- and stereo-determining.

Transition metal and base free synthesis of 2-aryl-2-oxazolines from aldehydes and β-amino alcohols catalysed by potassium iodide

Synthesis of 2-aryl-2-oxazolines from β-amino alcohols and aldehydes was achieved in good to excellent yield by employing a potassium iodide (KI)-tert-butyl hydroperoxide (TBHP) catalytic system. This protocol is very mild, metal and base free and can be performed under ambient reaction conditions. This oxidative cyclization strategy was further extended for the synthesis of optically active 2-oxazolines, which can act as very useful chiral auxiliaries and as ligands. This journal is

Nickel-catalyzed ligand-free synthesis of benzoxazoles and oxazolines via isocyanide insertion

A novel and efficient route to benzoxazoles and oxazolines involving a nickel-catalyzed three-component coupling reaction of iodobenzene, an amino alcohol and tert-butyl isocyanide has been developed. A wide array of products have been prepared in good to excellent yields in the absence of ligand.

Phosphine-catalyzed heine reaction

Aziridines are important synthetic intermediates which readily undergo ring-opening reactions. It is demonstrated that electron-rich phosphines are efficient catalysts for the regioselective rearrangement of N-acylaziridines to oxazolines. The reactions o

Effects of monodentate oxazoline ligands in Ni/Al-catalyzed regioselective cyclotrimerization of enones and alkynes

A nickel and aluminium system including monodentate oxazoline ligands catalyzed the regioselective cyclotrimerization of enones and alkynes.

Regioselectivity in Nucleophilic Ring Opening of 2-Methylaziridines. Lag of Bond Making as Model for the Abnormal Opening

The regioselectivity ratio RS=normal:abnormal opening of activated 2-methylaziridines 2 by nucleophiles is found to range from 0.10 to unmeasurable large (only normal opening=substitution at CH2 by strongly basic carbanions).RS is assumed to result from SN2 variants differing in the degree to which bond breaking is ahead of bond making including perhaps synchronous SN2.Bond breaking will be more ahead for the N-CMe bond.High nucleophilic power pushes bond making toward a synchronous process resulting in great RS.The decrease in RS with acyl activation relative to sulfonyl activation is in accord with a flattening of the nitrogen pyramid (planarization effect).The planarization effect is retained in acidic medium by O-protonation: RS 0.10-0.14 for methanolysis as compared to RS 0.43 for N-protonated sulfonylaziridine 2h.AM1 calculations support the planarization hypothesis. - No indication for SET with trityl anion was found.

The Conversion of an Aziridine to a β-Lactam

A one-pot, inert atmosphere conversion of an aziridine to a β-lactam using nickel tetracarbonyl as the carbonyl source is described.In this reaction it is the less substituted carbon-nitrogen bond which is carbonylated.The proposed mechanism for this reac