37055-29-1

Upstream product

• 576-83-0 2,4,6-trimethylphenyl bromide 
• 4028-63-1 iodomesitylene 
• 2633-66-1 2-mesitylmagnesium bromide 
• 852142-68-8 (η¹-mesityl)₂Fe(κ²-TMEDA) 
• 16873-17-9 deuterium 
• 108-67-8 1,3,5-trimethyl-benzene 
• 5980-97-2 mesitylboronic acid 
• 2206-26-0 [D₃]acetonitrile 
• 23897-15-6 tris(2,4,6-trimethylphenyl)phosphine 
• 1455-13-6 deuteromethanol 
• 1250409-79-0 2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-(2,4,6-trimethylphenyl)iodonium ylide 

Downstream Products

• 1332484-19-1 C₁₁H₁₃⁽²⁾HO₂ 
• 19082-49-6 mesityl acetate 
• 1332484-10-2 1-acetoxy-3-bromo-2,4,6-trimethylbenzene 
• 576-83-0 2,4,6-trimethylphenyl bromide 
• 1332484-20-4 C₉H₁₀⁽²⁾HBr 

Relevant academic research and scientific papers

Convenient synthetic method of functional phosphines under photochemical conditions

Steady-state photolysis of triarylphosphines, Ar3P, under an argon atmosphere in a solvent with the structure CH3X (X = CN, COOC2H5, COCH3) afforded an adduct with the solvent molecule, Ar2PCH2X, in significant amount. This photoreaction is acknowledged as a convenient method to prepare functional phosphines.

Activation and Oxidation of Mesitylene C-H Bonds by (Phebox)Iridium(III) Complexes

A pincer iridium(III) complex, (Phebox)Ir(OAc)2OH2 (1) (Phebox = 3,5-dimethylphenyl-2,6-bis(oxazolinyl)), selectively cleaves the benzylic C-H bond of mesitylene to form an isolable iridium mesityl complex, (Phebox)Ir(mesityl)(OAc) (3), in >90% yield. The trifluoroacetate analogue, (Phebox)Ir(OCOCF3)2OH2 (2), was synthesized to compare with complex 1 for C-H activation, and (Phebox)Ir(mesityl)(OCOCF3) (4) was synthesized by ligand exchange of complex 3. Both complexes 1 and 2 catalyze H/D exchange between mesitylene and D2O at 180 °C, exclusively at the benzylic position; 2 gave a higher turnover number (11 TO) than 1 (6 TO) in 12 h. Using d4-acetic acid as the source of deuterium, up to 92 turnovers of benzylic H/D exchange of mesitylene were obtained with complex 1. (Phebox)Ir(OCOCF3)2OH2 catalyzed the benzylic C-H oxidation of mesitylene using Ag2O as a terminal oxidant at 130 C, to form 3,5-dimethylbenzaldehyde and 3,5-dimethylbenzoic acid in 35% ± 4% yield (5.1 ± 0.6 TO). DFT calculations were used to investigate two possible pathways for the catalytic oxidation of mesitylene: (1) C-H activation followed by oxy-functionalization and (2) Ir-oxo formation followed by outer-sphere C-H hydroxylation. Results of calculations of the C-H activation pathway appear to be the more consistent with the experimental observations. (Chemical Equation Presented).

A capped trigonal pyramidal molybdenum hydrido complex and an unusually mild sulfur-carbon bond cleavage reaction

DFT calculations reveal that a reported molybdenum hydride complex has an unprecedented geometry with the molybdenum in the base of trigonal pyramid defined by three thiolate ligands with a phosphine ligand on the apex and a hydride capping a PS2 face. This complex reacts with methanol to produce a sulfido complex by a new reaction: the protonation of an ipso carbon of a thiolate ligand by coordinated methanol.

A stable but highly reactive phosphine-coordinated borenium: Metal-free dihydrogen activation and alkyne 1,2-carboboration

Borenium cations have been found to be valuable analogues of boranes as a result of their cationic character which imparts high electrophilicity. Herein, we report the synthesis, characterization, and reactivity of a new type of borenium cation employing a naphthyl bridge and a strong intramolecular P→B interaction. The cation reacts with H2 in the presence of PtBu3 (frustrated Lewis pair (FLP) approach) but also on its own. The mechanism of the reaction between the borenium cation and H2 in the absence of PtBu3 has been investigated using deuterium-labeling experiments and DFT calculations. Both experiments and calculations imply the side-on coordination of H2 to the B center, followed by heterolytic splitting and B-C bond cleavage. An uncommon syn 1,2-carboboration has also been observed upon reaction of the borenium ion with 3-hexyne. Versatile reactivity: A new type of borenium cation is reported in which a naphthyl bridge supports a strong P→B interaction. Borenium reacts with H2 through side-on coordination of H2 to boron, heterolytic splitting, and concomitant cleavage of the B-Mes bond. The molecule also reacts with 3-hexyne through a syn 1,2-carboboration reaction. NTf2-=triflimide.

Gold-Catalyzed Proto- and Deuterodeboronation

A mild gold-catalyzed protodeboronation reaction, which does not require acid or base additives and can be carried out in "green" solvents, is described. As a result, the reaction is very functional-group-tolerant, even to acid- and base-sensitive functional groups, and should allow for the boronic acid group to be used as an effective traceless directing or blocking group. The reaction has also been extended to deuterodeboronations for regiospecific ipso-deuterations of aryls and heteroaryls from the corresponding organoboronic acid. Based on density functional theory calculations, a mechanism is proposed that involves nucleophilic attack of water at boron followed by rate-limiting B-C bond cleavage and facile protonolysis of a Au-σ-phenyl intermediate.

Iron promoted conjugate addition: Implication of the six-centered mechanism based on the isolation of the iron-enolate intermediate

Treatment of (η1-mesityl)2Fe(κ2- TMEDA) (1′) with an α,β-unsaturated carbonyl compound results in 1,4-addition of the mesityl group to give an iron enolate 3 quantitatively. The Z-configuration of the enolate suggested the

Halogen-deuterium exchange reaction mediated by tributyltin hydride using THF-d8 as the deuterium source

A regioselective deuteration method for a wide variety of aromatic compounds using the halogen-deuterium exchange reaction initiated by Bu 3SnH using THF-d8 as the deuterium source was developed.

Cobalt-xantphos-catalyzed, LiCl-mediated preparation of arylzinc reagents from aryl iodides, bromides, and chlorides

A cobalt-Xantphos-catalyzed, LiCl-mediated system has been developed for the direct and expedient preparation of arylzinc reagents in THF from the corresponding aryl iodides, bromides, and chlorides. Owing to the use of THF as a versatile solvent, the thus-formed arylzinc reagents displayed a high degree of compatibility with a variety of conventional as well as newly emerging metal-catalyzed cross-coupling reactions.

Gold(III)-catalyzed direct acetoxylation of arenes with iodobenzene diacetate

AuCl3-catalyzed direct acetoxylation of electron-rich aromatic compounds has been achieved with iodobenzene diacetate as the acetoxylation reagent.

NO-CARRIER-ADDED NUCLEOPHILIC [F-18] FLUORINATION OF AROMATIC COMPOUNDS

Phenyliodonium ylide derivatives substituted with electron donating as well as electron withdrawing groups on the aromatic ring are shown for use as precursors in aromatic nucleophilic substitution reactions. The iodonium ylide group is substituted by nucleophiles such as halide ions to provide the corresponding haloaryl derivatives. No- carrier-added [F-18]fluoride ion exclusively substitutes the iodonium ylide moiety in these derivatives and provides high specific activity F- 18 labeled fluoro derivatives. Protected L-dopa-6-iodonium ylide derivative have been synthesized as a precursors for the preparation of no-carrier-added 6-[F- 18]fluoro-L-dopa. The iodonium ylide group in this L-dopa.derivative is nucleophilically substituted by no-carrier-added [F-18]fluoride ion to provide a [F-18]fluoro intermediates which upon acid hydrolysis yielded 6-[F- 18]fluoro-L-dopa.