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• 143925-38-6 N-(2-Propenyl)-N-phenylacrylamide 
• 332-77-4 2,5-dihydro-2,5-dimethoxyfuran 
• 142-04-1 aniline hydrochloride 
• 4641-57-0 1-phenylpyrrolidin-2-one 
• 600-17-9 vinyl glycolic acid 
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Relevant academic research and scientific papers

Employing α-Diazocarbonyl Compound Chemistry in the Assembly of Medicinally Important Aryl(alkyl)thiolactam Scaffold

RH2(OAc)4-catalyzed coupling of α-diazo-γ-butyrolactams with a wide range of aliphatic and aromatic thiols leads to α-aryl(alkyl)thiolactams in generally good yields. The transformation was found to be tolerant to sterically hindered thiols in contrast to analogous O–H insertion. Moreover, the same diazo lactams can be easily converted to β-aryl(alkyl)thiolactams in two steps using one-pot protocol. Consequently, the continued synthetic exploration of α-diazo-γ-butyrolactams paves the way toward two medicinally important scaffolds.

Synthetic Exploration of α-Diazo γ-Butyrolactams

DIazo transfer reaction onto γ-butyrolactams (activated by α-ethyloxalylation) gave rare α-diazo γ-butyrolactams. Decomposition of the latter by Rh2(OAc)4 in the presence of alcohols and water gave products of O–H insertion of the respective metal-cabene species. Silver triflate (1 mol-%) was found to convert the γ-butyrolactams investigated into 1,5-dihydro-2H-pyrrol-2-ones which represent versatile building blocks. Particular instability was noted for α-diazo γ-butyrolactams bearing alkyl or o-substituted aryl substituents on the nitrogen atom. These were found to dimerize in solution or upon storage at room temperature to give fully conjugated bis-hydrazones along with the loss of a nitrogen molecule.

Site-Selective Acceptorless Dehydrogenation of Aliphatics Enabled by Organophotoredox/Cobalt Dual Catalysis

The value of catalytic dehydrogenation of aliphatics (CDA) in organic synthesis has remained largely underexplored. Known homogeneous CDA systems often require the use of sacrificial hydrogen acceptors (or oxidants), precious metal catalysts, and harsh reaction conditions, thus limiting most existing methods to dehydrogenation of non- or low-functionalized alkanes. Here we describe a visible-light-driven, dual-catalyst system consisting of inexpensive organophotoredox and base-metal catalysts for room-temperature, acceptorless-CDA (Al-CDA). Initiated by photoexited 2-chloroanthraquinone, the process involves H atom transfer (HAT) of aliphatics to form alkyl radicals, which then react with cobaloxime to produce olefins and H2. This operationally simple method enables direct dehydrogenation of readily available chemical feedstocks to diversely functionalized olefins. For example, we demonstrate, for the first time, the oxidant-free desaturation of thioethers and amides to alkenyl sulfides and enamides, respectively. Moreover, the system's exceptional site selectivity and functional group tolerance are illustrated by late-stage dehydrogenation and synthesis of 14 biologically relevant molecules and pharmaceutical ingredients. Mechanistic studies have revealed a dual HAT process and provided insights into the origin of reactivity and site selectivity.

N -Acyliminium Ion Chemistry: Improving the Access to Unsaturated γ-Lactams and Their N -α-Methoxylated Derivatives: Application to an Expeditive Synthesis of (±)-Crispine A

An improved synthesis of unsaturated γ-lactams by condensation of various primary amines with 2,5-dimethoxy-2,5-dihydrofuran is described. A modified mechanism for this reaction is suggested. Synthesis of their N -α-methoxylated derivatives, as N -acyliminium ion precursors, is also reported. Finally, a short synthesis of (±)-crispine A is presented as an illustrative application.

Domino Synthesis of α,β-Unsaturated γ-Lactams by Stereoselective Amination of α-Tertiary Allylic Alcohols

Tertiary allylic alcohols equipped with a carboxyl group can be smoothly aminated under ambient conditions by a conceptually new and stereoselective protocol under palladium catalysis. The in situ formed Z-configured γ-amino acid cyclizes to afford an α,β-unsaturated γ-lactam, releasing water as the only byproduct. This practical catalytic transformation highlights the use of a carboxyl group acting as an activating and stereodirecting functional group to provide a wide series of pharma-relevant building blocks. Various control reactions support the crucial role of the carboxyl group in the substrate to mediate these transformations.

Convenient synthesis of α,β-unsaturated γ-butyrolactones and γ-butyrolactams via decarboxylative iodination of paraconic acids and β-carboxyl-γ-butyrolactams using 1,3-diiodo-5,5-dimethylhydantoin

A convenient synthetic approach to α,β-unsaturated γ-butyrolactones and α,β-unsaturated γ-butyrolactams is developed. The reaction proceeds via decarboxylative iodination of paraconic acids and β-carboxyl-γ-butyrolactams, employing 1,3-diiodo-5,5-dimethylhydantoin (DIH) under irradiation, followed by dehydroiodination of β-iodo-γ-butyrolactones and γ-butyrolactams providing good yields of α,β-unsaturated γ-butyrolactones and γ-butyrolactams, which are synthetically useful building blocks in organic synthesis.

Synthesis of nitrogen-containing heterocycles via ring-closing ene-ene and ene-yne metathesis reactions: An easy access to 1- and 2-benzazepine scaffolds and five- and six-membered lactams

Novel regioselective ring closing ene-yne metathesis provided an efficient access to different substituted 1-benzazepine scaffolds. The reported synthetic approach could also be used as a powerful tool for the selective formation of a highly functionaliza

A new route to N-aryl 2-alkenamides, N-allyl N-aryl 2-alkenamides, and N-aryl α,β-unsaturated γ-lactams from N-aryl 3-(phenylsulfonyl)propanamides

A series of N-aryl 2-alkenamides were produced efficiently by treating N-aryl 3-(phenylsulfonyl)-propanamides with potassium tert-butoxide in THF at 0°C. Without isolation, it was further treated with an additional equivalent of potassium tert-butoxide and allyl bromide to give N-allyl N-aryl 2-alkenamides in one pot in good yields. Followed by a ring-closing metathesis reaction, these N-allyl N-aryl 2-alkenamides were respectively converted into corresponding N-aryl α,β-unsaturated γ-lactams in moderate yields.

Ruthenium carbene complexes with N,N'-bis(mesityl)imidazol-2-ylidene ligands: RCM catalysts of extended scope

The ruthenium carbene complexes 3a,b bearing imidazol-2-ylidene ligands constitute excellent precatalysts for ring-closing metathesis (RCM) reactions allowing the formation of tri- and tetrasubstituted cycloalkenes. They also apply to annulations that are beyond the scope of the standard Grubbs carbene 1 as well as to ring-closing reactions of acrylic acid derivatives even if the resulting α,β-unsaturated lactones (or lactams) are tri- or tetrasubstituted. The reactivity of 3a was found to be highly dependent on the reaction medium: particularly high reaction rates are observed in toluene, although this solvent also leads to an increased tendency of the catalyst to isomerize the double bonds of the substrates.

DIRECT REGIO- AND STEREO-SELECTIVE LITHIATION OF SECONDARY ALLYL AND METHYLALLYL AMINES: A NEW TYPE OF γ-AMINATED ORGANOLITHIUM REAGENTS IN ORGANIC SYNTHESIS

Several secondary allyl and methylallylamines (6) have been regio- and stereo-selectively lithiated with t-butyl-lithium, giving the corresponding sp2 γ-aminated organolithium intermediates (7), which by reaction with electrophiles D2O, Me2S2,