36808-96-5

Upstream product

• 645-45-4 hydrocinnamic acid chloride 
• 501-52-0 3-Phenylpropionic acid 
• 497-03-0 2-methylbut-2-enal 
• 90878-19-6 phenethylmagnesium chloride 
• 181573-12-6 (+/-)-(E)-4-methyl-1-phenylhex-4-en-3-ol 
• 671795-46-3 sec-butylmagnesium bromide 
• 598-30-1 sec.-butyllithium 
• 43125-15-1 3-phenyl-S-(2'-pyridyl) thiopropionate 

Relevant academic research and scientific papers

Radical-Based C?C Bond-Forming Processes Enabled by the Photoexcitation of 4-Alkyl-1,4-dihydropyridines

We report herein that 4-alkyl-1,4-dihydropyridines (alkyl-DHPs) can directly reach an electronically excited state upon light absorption and trigger the generation of C(sp3)-centered radicals without the need for an external photocatalyst. Selective excitation with a violet-light-emitting diode turns alkyl-DHPs into strong reducing agents that can activate reagents through single-electron transfer manifolds while undergoing homolytic cleavage to generate radicals. We used this photochemical dual-reactivity profile to trigger radical-based carbon–carbon bond-forming processes, including nickel-catalyzed cross-coupling reactions.

Synergistic Photoredox/Nickel Coupling of Acyl Chlorides with Secondary Alkyltrifluoroborates: Dialkyl Ketone Synthesis

Visible light photoredox/nickel dual catalysis has been employed in the cross-coupling of acyl chlorides with potassium alkyltrifluoroborates. This protocol, based on single-electron-mediated alkyl transfer, circumvents the restriction of using reactive alkylmetallic nucleophiles in transition-metal-catalyzed acylation and achieves a mild and efficient method for the synthesis of unsymmetrical alkyl ketones. In this approach, a variety of acyl chlorides have been successfully coupled with structurally diverse potassium alkyltrifluoroborates, generating the corresponding ketones with good yields.

Synergistic Visible-Light Photoredox/Nickel-Catalyzed Synthesis of Aliphatic Ketones via N-C Cleavage of Imides

An electrophilic, imide-based, visible-light-promoted photoredox/Ni-catalyzed cross-coupling reaction for the synthesis of aliphatic ketones has been developed. This protocol proceeds through N-C(O) bond activation, made possible through the lower activation energy for metal insertion into this bond due to delocalization of the lone pair of electrons on the nitrogen by electron-withdrawing groups. The operationally simple and mild cross-coupling reaction is performed at ambient temperature and exhibits tolerance for a variety of functional groups.

General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand

Remarkably simple IrIIIcatalysts enable the isomerization of primary and sec-allylic alcohols under very mild reaction conditions. X-ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*IrIII], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.

Synthesis of α-methyl ketones by a selective, iridium-catalyzed cyclopropanol ring-opening reaction

A mild method for synthesizing α-methyl ketones from substituted cyclopropanols is reported. This process, catalyzed by [CpIrCl2] 2, cleaves cyclopropanol rings regioselectively and more efficiently than the other conditions examined. While tertiary cyclopropanols afford α-methyl ketones, secondary cyclopropanols and cyclopropyl silyl ethers are less reactive and yield other isomerization products.

Acylation of α-(N-carbamoyl)alkylcuprates and alkyl- or aryl(halo)cuprates

α-(N-Carbamoyl)alkylcuprates [R2CuLi·LiX or RCuXLi (X=CN, Cl)] when prepared from THF soluble CuX·2LiCl (X=Cl, CN) undergo a reliable and generally high yield reaction with aroyl, alkanoyl, and alkenoyl chlorides to provide a rapid and efficient synthesis of α-carbamoyl ketones. Cuprates prepared from acyclic, cyclic, and a functionalized carbamate can be utilized. Although yields are a function of cuprate reagent and substrate structure, nearly quantitative yields can be obtained with reagents generated from 2RLi+CuCN·2LiCl. The use of reagents generated from CuCl·2LiCl are more efficient in the α-(N-carbamoyl)alkyl ligand, although yields are slightly lower. Acylation of alkyl(chloro)cuprates generated from one equivalent of CuCl·2LiCl and organolithium or Grignard reagents provides an efficient and high yield procedure for ketone synthesis.

Acylation of α-aminoalkyl- copper and cuprate reagents with acid chlorides: Improved yields with soluble copper (I) salts

α-Aminoalkylcopper reagents prepared from soluble CuX·2LiCI give modest to good yields of α-aminoketones upon reaction with acid chlorides, Higher yields are generally obtained with CuCl·2LiCl than with CuCN·2LiCl. Improved yields can be obtained by utilization of cuprate reagents prepared from CuCN·2LiCl and 2.0 equivalents of α-lithiocarbamates.