93315-97-0

Upstream product

• 85-44-9 phthalic anhydride 
• 88-05-1 2,4,6-trimethylaniline 
• 108-67-8 1,3,5-trimethyl-benzene 
• 422508-64-3 1,3-dioxoisoindolin-2-yl 2,3,4,5,6-pentafluorobenzoate 
• 5672-90-2 N-(trifluoromethyl)acyloxyphthalimide 
• 524-38-9 N-hydroxyphthalimide 
• 136918-14-4 phthalimide 
• 1875-48-5 N-aminophthalamide 
• 59344-64-8 tris(2,4,6-trimethylphenyl)bismuth 

Downstream Products

• 85-44-9 phthalic anhydride 
• 88-05-1 2,4,6-trimethylaniline 

Relevant academic research and scientific papers

Cyclic (aryl)(amido)carbenes: Pushing the π-acidity of amidocarbenes through benzannulation

Cyclic(aryl)(amido)carbenes were synthesized, and studied via a combination of experimental and computational approaches. These carbenes undergo dimerization when isolation is attempted, however, are trapped with sulfur, selenium, and [Ir(cod)Cl]. The π-acidity, measured using 77Se NMR, revealed that these are the most electrophilic singlet carbenes reported to date whereas the TEP measured demonstrated that these carbenes are poor σ donors.

A phosphonium ylide as a visible light organophotoredox catalyst

A phosphonium ylide-based visible light organophotoredox catalyst has been designed and successfully applied to halohydrin synthesis using trichloroacetonitrile and epoxides. An oxidative quenching cycle by the ylide catalyst was established, which was confirmed by experimental mechanistic studies.

Metal-to-Ligand Ratio-Dependent Chemodivergent Asymmetric Synthesis

Chemodivergent asymmetric synthesis was achieved by tuning the metal-to-ligand ratio in an organometallic catalytic system. Using N-(aroyloxy)phthalimide as the precursor of either an oxygen-centered aroyloxy radical or a nitrogen-centered phthalimidyl radical, enantioselective oxocyanation or aminocyanation of alkenes was achieved separately through a dual photoredox and copper catalysis. The metal-to-ligand ratio can exert chemoselective control while retaining the high enantiopurity of divergent products. Both reactions proceed efficiently with catalyst loading as low as 0.2 mol % and can be performed on a gram scale without loss of chemoselectivity or enantioselectivity. Chemodivergent asymmetric 1,5-aminocyanation or 1,5-oxocyanation of vinylcyclopropane can also be realized by this protocol. Mechanistic investigations involving electron paramagnetic resonance (EPR) experiments were performed to shed light on the stereochemical and chemodivergent results.

Visible-Light-Induced Metal-/Photocatalyst-Free C-H Bond Imidation of Arenes

In this study, a visible-light-induced intermolecular C-H bond imidation of arenes was achieved at ambient condition. By using simple phthalimide with (diacetoxyiodo)benzene and molecular iodine, direct metal-/photocatalyst-free C-N bond formation was achieved. The imidation protocol was designed by using time-dependent density functional theory calculations and experimentally demonstrated for 28 substrates with as high as 96% yield. Mechanistic studies indicated that radical-mediated aromatic substitution occurred via photolysis of N-iodophthalimide under visible-light irradiation.

Cyclic (Aryl)(Amido)Carbenes: NHCs with Triplet-like Reactivity

The synthesis and study of a library of cyclic (aryl)(amido)carbenes (CArAmCs), which represent a class of electrophilic NHCs that feature low calculated singlet-triplet gaps (ΔEST=19.9 kcal mol?1; B3LYP/def2-TZVP) and exhibit reactivity profiles expected from triplet carbenes, are described. The electrophilic properties of the CArAmCs were quantified by analyzing their respective selenium adducts, which exhibited the largest downfield 77Se NMR chemical shifts (up to 1645 ppm) measured for any NHC derivative known to date, as well as their Ir carbonyl complexes, from which large Tolman electronic parameter (TEP) values (up to 2064 cm?1) were ascertained. The CArAmCs were found to engage in reactions that are typically observed with triplet carbenes, including C?H insertions, [2+1] cycloadditions with alkenes as well as alkynes, and spontaneous oxidation upon exposure to oxygen.

Revisiting phosphorus analogues of phthalimides and naphthalimides: Syntheses and comparative studies

A series of phosphorus analogues of aromaticfused monoimides (phthalimides and naphthalimides) bearing a mesityl group on the P center have been synthesized. In a comparison of their photophysical, electrochemical, and thermal properties with those of the corresponding imides, the impact of P incorporation was revealed. Furthermore, theoretical studies using DFT methods were conducted to understand their properties.

N -aminopyridinium salts as precursors for N-centered radicals - Direct amidation of arenes and heteroarenes

Readily prepared N-aminopyridinium salts are valuable precursors for the generation of N-centered radicals. Reduction of these salts by single electron transfer allows for clean generation of amidyl radicals. It is shown that direct radical C-H amination of heteroarenes and arenes can be achieved with N-aminopyridinium salts under mild conditions by using photoredox catalysis.

Nitrogen-centered radical-mediated C-H imidation of arenes and heteroarenes via visible light induced photocatalysis

The C-H imidation of arenes and heteroarenes has been achieved via visible light induced photocatalysis. In the presence of an iridium(iii) photoredox catalyst, the reaction of aromatic substrates with N-chlorophthalimide furnishes the N-aryl products at room temperature through a nitrogen-centered radical mediated aromatic substitution.

N-acyloxyphthalimides as nitrogen radical precursors in the visible light photocatalyzed room temperature C-H amination of arenes and heteroarenes

This paper reports a room temperature visible light photocatalyzed method for the C-H amination of arenes and heteroarenes. A key enabling advance in this work is the design of N-acyloxyphthalimides as precursors to nitrogen-based radical intermediates for these transformations. A broad substrate scope is presented, including the selective meta-amination of pyridine derivatives. A radical aromatic substitution mechanism is proposed.

Intermolecular oxidative C-N bond formation under metal-free conditions: Control of chemoselectivity between aryl sp2 and benzylic sp 3 C-H bond imidation

A new synthetic approach toward intermolecular oxidative C-N bond formation of arenes has been developed under transition-metal-free conditions. Complete control of chemoselectivity between aryl sp2 and benzylic sp 3 C-H bond imidation was achieved by the choice of nitrogen sources, representatively being phthalimide and dibenzenesulfonimide, respectively.