56229-85-7

Upstream product

• 3977-92-2 (+/-)-(1S,2S)-N,N-diethyl-2-phenylcyclopropanocarboxamide 
• 141377-53-9 1-nitro-4-phenylbutan-2-ol 
• 80922-14-1 1-nitro-4-phenylbut-1-ene 
• 78579-86-9 1-nitro-4-phenylbutane 
• 109-89-7 diethylamine 
• 104-53-0 3-phenyl-propionaldehyde 
• 1821-12-1 4-Phenylbutyric acid 
• 18496-54-3 phenylbutyric acid chloride 
• 2315-36-8 2-Chloro-N,N-diethylacetamide 
• 996-86-1 N,N-diethyl-2-sulfanylacetamide 
• 100-52-7 benzaldehyde 
• 19493-09-5 Methylenetriphenylphosphorane 
• 121-44-8 triethylamine 
• 100-42-5 styrene 

Downstream Products

• 34329-63-0 N-(4-methoxyphenyl)-4-phenylbutanamide 
• 430459-99-7 C₁₇H₁₉NO 
• 61123-41-9 N,N-Dibutyl-4-phenyl-butyramide 
• 6876-67-1 4-Phenyl-N-p-tolyl-butyramide 
• 78172-94-8 N-benzyl-N-methyl-4-phenylbutanamide 
• 430457-82-2 C₁₅H₂₁NO 
• 64353-78-2 4-phenyl-butyric acid cyclohexylamide 
• 885912-44-7 N-hexyl-4-phenylbutanamide 
• 382176-84-3 C₁₃H₁₄N₂OS 
• 3056-71-1 N-phenyl-4-phenylbutyramide 
• 121189-73-9 N-Benzothiazol-2-yl-4-phenyl-butyramide 
• 412945-90-5 C₂₀H₁₉NO 

Relevant academic research and scientific papers

Visible-light induced metal-free cascade Wittig/hydroalkylation reactions

Cascade reactions are green and powerful transformations for building multiple carbon-carbon bonds in one step. Through a relay olefination and radical addition process, we were able to develop the cascade Wittig/hydroalkylation reactions induced by visible light. This metal-free radical approach features mild conditions, robustness, and excellent functionality compatibility. It allows access to saturated C3 homologation products directly from aldehydes or ketones. The synthetic utility of this method is demonstrated by a two-step synthesis ofindolizidine 209D.

Palladium-Catalyzed N-Acylation of Tertiary Amines by Carboxylic Acids: A Method for the Synthesis of Amides

A palladium-catalyzed N-acylation of tertiary amines by carboxylic acids was achieved through C-N cleavage. This reaction showed a wide substrate scope. Both aromatic and aliphatic acids served well as the acylating reagents and coupled with tertiary amines to produce the corresponding amides in good to excellent yields. With the strategy, bioactive carboxylic acids were also efficiently modified, highlighting the synthetic value of the process in organic synthesis.

C-Alkylation of N-alkylamides with styrenes in air and scale-up using a microwave flow reactor

C-Alkylation of N-alkylamides with styrenes is reported, proceeding in ambient air/moisture to give arylbutanamides and pharmaceutically-relevant scaffolds in excellent mass balance. Various amide and styrene derivatives were tolerated, rapidly affording molecular complexity in a single step; thus highlighting the future utility of this transformation in the synthetic chemistry toolbox. Reaction scalability (up to 65 g h-1 product) was demonstrated using a Microwave Flow reactor, as the first example of a C-alkylation reaction using styrenes in continuous flow.

Iodobenzene Dichloride in the Esterification and Amidation of Carboxylic Acids: In-Situ Synthesis of Ph3PCl2

A novel, in-situ synthesis of dichlorotriphenylphosphorane (Ph3PCl2) is accomplished upon combining PPh3and the easily prepared hypervalent iodine reagent iodobenzene dichloride (PhICl2). The phosphorane is selectively generated in the presence of carboxylic acid or alcohol residues to rapidly produce acyl chlorides and alkyl chlorides in high yields. Addition of EtOH, PhOH, BnOH, Et2NH or CH2N2results in the direct synthesis of esters, amides and diazo ketones from carboxylic acids.

Oxidative Amidation of Nitroalkanes with Amine Nucleophiles using Molecular Oxygen and Iodine

The formation of amides and peptides often necessitates powerful yet mild reagent systems. The reagents used, however, are often expensive and highly elaborate. New atom-economical and practical methods that achieve such goals are highly desirable. Ideally, the methods should start with substrates that are readily available in both chiral and non-chiral forms and utilize cheap reagents that are compatible with a wide variety of functional groups, steric encumberance, and epimerizable stereocenters. A direct oxidative method was developed to form amide and peptide bonds between amines and primary nitroalkanes simply by using I2 and K2CO3 under O2. Contrary to expectations, a 1:1 halogen-bonded complex forms between the iodonium source and the amine, which reacts with nitronates to form α-iodo nitroalkanes as precursors to the amides.

Mechanism of SmI2/amine/H2O-promoted chemoselective reductions of carboxylic acid derivatives (esters, acids, and amides) to alcohols

Samarium(II) iodide-water-amine reagents have emerged as some of the most powerful reagents (E° = -2.8 V) for the reduction of unactivated carboxylic acid derivatives to primary alcohols under single electron transfer conditions, a transformation that had been considered to lie outside the scope of the classic SmI2 reductant for more than 30 years. In this article, we present a detailed mechanistic investigation of the reduction of unactivated esters, carboxylic acids, and amides using SmI2-water-amine reagents, in which we compare the reactivity of three functional groups. The mechanism has been studied using the following: (i) kinetic, (ii) reactivity, (iii) radical clock, and (iv) isotopic labeling experiments. The kinetic data indicate that for the three functional groups all reaction components (SmI2, amine, water) are involved in the rate equation and that the rate of electron transfer is facilitated by base assisted deprotonation of water. Notably, the mechanistic details presented herein indicate that complexation between SmI2, water, and amines can result in a new class of structurally diverse, thermodynamically powerful reductants for efficient electron transfer to a variety of carboxylic acid derivatives. These observations will have important implications for the design and optimization of new processes involving Sm(II)-reduction of ketyl radicals. (Chemical Equation Presented).

Highly chemoselective reduction of amides (primary, secondary, tertiary) to alcohols using SmI2/amine/H2O under mild conditions

Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C-N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C-O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → πC=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C-N/C-O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions.

Effective acceleration of atom transfer carbonylation of alkyl iodides by metal complexes. Application to the synthesis of the hinokinin precursor and dihydrocapsaicin

Atom transfer carbonylation (ATC) of alkyl iodides leading to carboxylic acid esters is effectively accelerated by Pd(PPh3)4 and Mn2(CO)10 under photoirradiation conditions. In the presence of amines, Pd(0) complexes affected double carbonylations leading to α-keto amides, whereas Mn2(CO)10 accelerated only a single carbonylation reaction leading to the corresponding amides. The Pd(0)-accelerated ATC system was successfully applied to the synthesis of hinokinin and dihydrocapsaicin.

Cross-coupling reactions of carbamoyl chlorides and Grignard reagents: A new rapid synthesis of tertiary amides

Tributyl phosphine or nickel catalysts allow the cross-coupling reaction between N,N-dialkylcarbamoyl chlorides and alkyl or aryl Grignard reagents. This convenient and simple method affords tertiary amides with moderate to excellent yields in short reaction times. (C) 2000 Elsevier Science Ltd.