41763-91-1

Upstream product

• 1197-18-8 trans-4-aminomethyl-cyclohexyl-carboxylic acid 
• 766-05-2 cyclohexane carbonitrile 
• 612-14-6 phthalyl alcohol 
• 881588-23-4 N-(cyclohexylmethyl)-2-iodobenzamide 
• 1864-94-4 phenyl formate 
• 136918-14-4 phthalimide 
• 100-49-2 cyclohexylmethyl alcohol 
• 524-38-9 N-hydroxyphthalimide 
• 3218-02-8 cyclohexylmethylamine 
• 615-42-9 1,2-Diiodobenzene 
• 201230-82-2 carbon monoxide 
• 85-44-9 phthalic anhydride 
• 80191-01-1 (1R*,4R*)-4-((1,3-dioxoisoindolin-2-yl)methyl)cyclohexane-1-carboxylic acid 

Relevant academic research and scientific papers

Time-resolved spectroscopy of sulfur- and carboxy-substituted N-alkylphthalimides

The photophysical and photochemical properties of N-phthaloylmethionine (1), S-methyl-N-phthaloylcysteine methyl ester (2) and N-phthaloyltranexamic acid (3) were studied by time-resolved UV/Vis spectroscopy, using laser pulses at 248 or 308 nm. The quant

One-Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride

The Mitsunobu reaction is a powerful transformation for the one-pot activation and substitution of aliphatic alcohols. Significant efforts have focused on modifying the classic conditions to overcome problems associated with purification from phosphine-based byproducts. Herein, we report a phosphine free method for alcohol activation and substitution that is mediated by sulfuryl fluoride. This new method is effective for a wide range of primary alcohols using phthalimide, di-tert-butyl-iminodicarboxylate, and aromatic thiol nucleophiles in 74 % average yield. Activated carbon nucleophiles and a deactivated phenol were also effective for this reaction in good yields. Secondary alcohols were also successful substrates using aryl thiols, affording the corresponding sulfides in 56 % average yield with enantiomeric ratios up to 99:1. This new protocol has a distinct synthetic advantage over many existing phosphine-based methods as the byproducts are readily separable. This feature was exploited in several examples that did not require chromatography for purification. Furthermore, the mild reaction conditions enabled further in situ derivatization for the one-pot conversion of alcohols to amines or sulfones. This method also provides a boarder nucleophile scope compared to existing phosphine-free methods.

Photochemical Decarboxylative C(sp3)-X Coupling Facilitated by Weak Interaction of N-Heterocyclic Carbene

While N-hydroxyphthalimide (NHPI) ester has emerged as a powerful reagent as an alkyl radical source for a variety of C-C bond formations, the corresponding C(sp3)-N bond formation is still in its infancy. We demonstrate herein transition-metal-free decarboxylative C(sp3)-X bond formation enabled by the photochemical activity of the NHPI ester-NaI-NHC complex, giving primary C(sp3)-(N)phth, secondary C(sp3)-I, or tertiary C(sp3)-(meta C)phth coupling products. The primary C(sp3)-(N)phth coupling offers convenient access to primary amines.

Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide

Adamantane α-, β-, and δ-amino acids activated by phthalimide (i.e., 3–6) were synthesized, and their photochemical reactivities were investigated. Amino acid derivatives 3–6 underwent a photoinduced electron transfer (PET) and decarboxylation reaction sequence, most probably through a triplet excited state. The decarboxylations of the β-amino acid derivatives were succeeded by cyclization reactions that afforded complex polycyclic molecules with potential biological interest. The adamantyl radical that is produced by the photoinduced decarboxylation could be trapped by alkenes or oxygen to deliver adducts or alcohols, respectively. The photodecarboxylation process was shown to be more efficient under acetone sensitization conditions (with quantum yields, Φ = 0.02–0.5) than upon direct excitation, and the reactivity was dependent on the chain length (intramolecular distance) between the electron donor (carboxylate) and acceptor (phthalimide in the triplet excited state) of the derivative. The formation of different radicals, that is, the 1- or 2-adamantyl intermediate, probably does not affect the overall rate of the decarboxylation This current report provides a better understanding of photodecarboxylation and the rational design of molecular systems to undergo photoinduced decarboxylation and cyclization reactions.

Transamidation catalysed by a magnetically separable Fe3O4 nano catalyst under solvent-free conditions

An environmentally benign protocol for transamidation of carboxamides with different amines under solvent free conditions using magnetically separable nano Fe3O4 as a heterogeneous catalyst is developed. The series of aryl and alkyl amines with long chain alkyl substituents have been selectively converted into transamide products. The current protocol offers a diverse substrate scope with good yield of the product. The Fe3O4 nano catalyst has also been used for formylation of amines via transamidation of dimethyl formamide. Efficient transamidation, ease of work up, simple separation and reusability of the catalyst for up to six runs are the important highlights of this process.

Carbonylative synthesis of phthalimides and benzoxazinones by using phenyl formate as a carbon monoxide source

A simple and efficient palladium-catalyzed carbonylative cyclization of N-substituted 2-iodobenzamides and 2-iodoanilides was investigated for the synthesis of phthalimides and benzoxazinones, respectively, by using phenyl formate as a CO source. The present catalytic protocol circumvents the use of an expensive phosphine ligand as well as solvent in the case of the phthalimide synthesis. Moreover, mild reaction conditions and a tolerance of various functional groups enhance the general applicability of this method.

Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives via Organic Photoredox Catalysis: Substrate Scope and Mechanistic Insight

A direct, catalytic hydrodecarboxylation of primary, secondary, and tertiary carboxylic acids is reported. The catalytic system consists of a Fukuzumi acridinium photooxidant with phenyldisulfide acting as a redox-active cocatalyst. Substoichiometric quantities of Hünigs base are used to reveal the carboxylate. Use of trifluoroethanol as a solvent allowed for significant improvements in substrate compatibilities, as the method reported is not limited to carboxylic acids bearing α heteroatoms or phenyl substitution. This method has been applied to the direct double decarboxylation of malonic acid derivatives, which allows for the convenient use of dimethyl malonate as a methylene synthon. Kinetic analysis of the reaction is presented showing a lack of a kinetic isotope effect when generating deuterothiophenol in situ as a hydrogen atom donor. Further kinetic analysis demonstrated first-order kinetics with respect to the carboxylate, while the reaction is zero-order in acridinium catalyst, consistent with another finding suggesting the reaction is light limiting and carboxylate oxidation is likely turnover limiting. Stern-Volmer analysis was carried out in order to determine the efficiency for the carboxylates to quench the acridinium excited state.

Synthesis of cyclic imides from nitriles and diols using hydrogen transfer as a substrate-activating strategy

An atom-economical and versatile method for the synthesis of cyclic imides from nitriles and diols was developed. The method utilizes a Ru-catalyzed transfer-hydrogenation reaction in which the substrates, diols, and nitriles are simultaneously activated into lactones and amines in a redox-neutral manner to afford the corresponding cyclic imides with evolution of H2 gas as the sole byproduct. This operationally simple and catalytic synthetic method provides a sustainable and easily accessible route to cyclic imides.

Immobilized palladium metal containing ionic liquid catalyzed one step synthesis of isoindole-1,3-diones by carbonylative cyclization reaction

Immobilized palladium metal containing ionic liquid (ImmPd-IL) catalyzed carbonylative cyclization reaction of 2-iodobenzoic acid and primary amine provided N-substituted isoindole-1,3-dione derivatives in good to excellent yield. The influence of various reaction parameters including the effect of base, solvent, temperature, time and CO pressure on carbonylative cyclization reaction using ImmPd-IL catalyst was investigated. Using optimized reaction parameters different aromatic, aliphatic and heterocyclic N-substituted isoindole-1,3-dione derivatives were synthesized from corresponding aryl amines. The developed protocol is heterogeneous, phosphine free and requires attainable reaction conditions like atmospheric CO pressure and lesser reaction time. The scope of the developed protocol was also extended for the synthesis of N-substituted isoindole-1,3-diones from methyl-2-iodobenoate and 1,2-diiodo benzene. The ImmPd-IL catalyst was recyclable up to four consecutive cycles and recycled catalyst was characterized by XPS analysis.

Photochemical transformations of proteinogenic and non-proteinogenic amino acids

The photochemistry of N-activated enantiomerically pure α-amino acids is described with emphasis on chemo-, regio-, stereo-, and spin selectivity. An especially valuable chromophore is the phthalimido group. The first excited singlet states are short-lived and deactivated (chemically) via homolytic CH cleavage or (physically) via electron-transfer steps. The first excited triplet states are chemically deactivated via electron-transfer reactions and subsequent deprotonation/coupling steps. A wide variety of product types were synthesized, and potential target molecules were available by tuning the reaction conditions. Also remote groups can be activated by means of electron-transfer steps, which represents an attractive new synthetic protocol for macrocyclization.