4215-86-5

Upstream product

• 100-41-4 ethylbenzene 
• 115-11-7 isobutene 
• 75553-24-1 (Z)-2-methyl-5-phenylpent-2-en-1-ol 
• 100-42-5 styrene 
• 920-36-5 (2-methylpropyl)lithium 
• 107-82-4 i-pentyl bromide 
• 5674-02-2 2-methylpropylmagnesium chloride 
• 103-63-9 1-phenyl-2-bromoethane 
• 2307-69-9 toluene-4-sulfonic acid isopropyl ester 
• 637-59-2 1-Bromo-3-phenylpropane 
• 121163-85-7 2-isopropyl-2-(2-phenethyl)-1,3-benzodithiole-1,1,3,3-tetraoxide 
• 75553-25-2 (E)-2-Methyl-5-phenyl-2-penten-1-ol 
• 4830-97-1 1,1-dimethyl-4-phenylbutyl chloride 
• 13556-76-8 1.2-Dichlor-4-methyl-pentan 

Downstream Products

• 1591939-46-6 2,2,3,3,3-pentafluoropropyl (4-methyl-1-phenylpentyl)sulfamate 

Relevant academic research and scientific papers

Intermolecular Radical C(sp3)?H Amination under Iodine Catalysis

The direct amination of aliphatic C?H bonds has remained one of the most tantalizing transformations in organic chemistry. Herein, we report on a unique catalyst system, which enables the elusive intermolecular C(sp3)?H amination. This practical synthetic strategy provides access to aminated building blocks and fosters innovative multiple C?H amination within a new approach to aminated heterocycles. The synthetic utility is demonstrated by the synthesis of four relevant pharmaceuticals.

Synthesis of quinolinyl-based pincer copper(ii) complexes: an efficient catalyst system for Kumada coupling of alkyl chlorides and bromides with alkyl Grignard reagents

Quinolinamide-based pincer copper(ii) complexes, κN,κN,κN-{C9H6N-(μ-N)-C(O)CH2NEt2}CuX [(QNNNEt2)CuX (X = Cl, 2; X = Br, 3; X = OAc, 4)], were synthesized by the reaction of ligand (QNNNEt2)-H (1) with CuX2 (X = Cl, Br or OAc) in the presence of Et3N. The reaction of (QNNNEt2)-H with CuX (X = Cl, Br or OAc) also afforded the Cu(ii) complexes 2, 3 and 4, respectively, instead of the expected Cu(i) pincer complexes. The formation of Cu(ii) complexes from Cu(i) precursors most likely occurred via the disproportionation reaction of Cu(i) into Cu(0) and Cu(ii). A cationic complex [(QNNNEt2)Cu(CH3CN)]OTf (5) was synthesized by the treatment of neutral complex 2 with AgOTf. On the other hand, the reaction of (QNNNEt2)-H (1) with [Cu(MeCN)4]ClO4 produced cationic Cu(i) complex, [(QNN(H)NEt2)Cu(CH3CN)]ClO4 (6), in good yield. All complexes 2-5 were characterized by elemental analysis and HRMS measurements. Furthermore, the molecular structures of 2, 3 and 4 were elucidated by X-ray crystallography. Complex 4 crystallizes in a dimeric and catemeric pattern. The cationic complex 5 was found to be an efficient catalyst for the Kumada coupling reaction of diverse nonactivated alkyl chlorides and bromides with alkyl magnesium chloride under mild reaction conditions.

Efficient phosphine-mediated formal C(sp3)-C(sp3) coupling reactions of alkyl halides in batch and flow

The construction of C(sp3)-C(sp3) bond is an essential chemical transformation in synthetic chemistry due to its abundance in organic scaffolds. Here we demonstrate a valuable adaptation of the Wittig-type chemical procedure to efficiently facilitate C(sp3)-C(sp3) bond formation utilizing a range of alkyl building blocks. Additionally the method is amenable with flow synthesis to afford coupled products in good to excellent yields without laborious purification process.

Analyzing site selectivity in Rh2(esp)2-catalyzed intermolecular C-H amination reactions

Predicting site selectivity in C-H bond oxidation reactions involving heteroatom transfer is challenged by the small energetic differences between disparate bond types and the subtle interplay of steric and electronic effects that influence reactivity. Herein, the factors governing selective Rh 2(esp)2-catalyzed C-H amination of isoamylbenzene derivatives are investigated, where modification to both the nitrogen source, a sulfamate ester, and substrate are shown to impact isomeric product ratios. Linear regression mathematical modeling is used to define a relationship that equates both IR stretching parameters and Hammett σ+ values to the differential free energy of benzylic versus tertiary C-H amination. This model has informed the development of a novel sulfamate ester, which affords the highest benzylic-to-tertiary site selectivity (9.5:1) observed for this system.

Cross-coupling of alkyl halides with aryl or alkyl Grignards catalyzed by dinuclear Ni(ii) complexes containing functionalized tripodal amine-pyrazolyl ligands

Structurally distinctive dinuclear Ni(ii) complexes with furan or thiophene tethered amine-pyrazolyl tripodal hybrid ligands have been synthesized and crystallographically characterized. All complexes are catalytically active towards cross-coupling of aryl/alkyl Grignard reagents with β-H containing alkyl halides at room temperature in the presence of N,N,N',N'- tetramethylethylenediamine (TMEDA). The catalytic efficacy of the complexes is dependent on the tether substituent at the central amine. Two species, Ni(ii) TMEDA and Mg(ii) TMEDA complexes, have been isolated from the catalytic reaction mixtures under different conditions. Some ligand-stabilized Ni(ii) and Mg(ii) bimetallic species have also been identified in the ESI-MS spectra.

Nickel complexes of a pincer amidobis(amine) ligand: Synthesis, structure, and activity in stoichiometric and catalytic C-C bond-forming reactions of alkyl halides

The synthesis, properties, and reactivity of nickel(II) complexes of a newly developed pincer amidobis(amine) ligand (McNN2) are described. Neutral or cationic complexes [(MeNN2)NiX] (X = OTf (6), OC(O)CH3 (7), CH3CN (8), OMe (9)) were prepared by salt metathesis or chloride abstraction from the previously reported [( MeNN2)NiCl] (1). The Lewis acidity of the {( McNN2)Ni) fragment was measured by the 1H NMR chemical shift of the coordinated CH3CN molecule in 8. Electrochemical measurements on 1 and 8 indicate that the electron-donating properties of NN2 are similar to those of the analogous amidobis(phosphine) (pnp) ligands. The solid-state structures of 6-8 were determined and compared to those of 1 and [(MeNN2)NiEt] (3). In all complexes, the MeNN2 ligand coordinates to the NiII ion in a mer fashion, and the square-planar coordination sphere of the metal is completed by an additional donor. The coordination chemistry of MeNN 2 thus resembles that of other three-dentate pincer ligands, for example, pnp and arylbis(amine) (ncn). Reactions of 2 with alkyl monohalides, dichlorides, and trichlorides were investigated. Selective C-C bond formation was observed in many cases. Based on these reactions, efficient Kumada-Corriu-Tamao coupling of unactivated alkyl halides and alkyl Grignard reagents with 1 as the precatalyst was developed. Good yields were obtained for the coupling of primary and secondary iodides and bromides. Double C-C coupling of CH2Cl2 with alkyl Grignard reagents by 1 was also realized. The scope and limitations of these transformations were studied. Evidence was found for a radical pathway in Ni-catalyzed C-C cross-coupling reactions, which involves NiIl alkyl intermediates.

Bicyclic nucleoside inhibitors of Varicella-Zoster virus: The effect of branching in the p-alkylphenyl side chain

Further to the discovery of bicyclic furanopyrimidine nucleoside analogues (BCNAs) as potent anti-VZV agents, a branched series of this family of compounds was synthesised. The aim was to study the impact of the geometry and steric hindrance in the side c

Radical deoxygenation of hydroxyl groups via phosphites

A highly efficient, two-step sequence method for the deoxygenation of hydroxyl groups has been developed. The method involves the preparation of the 2-(2-iodophenyl)ethyl methyl phosphite derivative of an alcohol using methyl dichlorophosphite and 2-(2-iodophenyl)ethanol. Treatment of the phosphite intermediate with (n-Bu)3SnH/AIBN in refluxing benzene cleanly produces the deoxygenation product of the original alcohol. Copyright

Formation of cyclopropanes by the reductive coupling of 1,3-dihalides promoted by titanocene(II) species

The treatment of various 1,3-dihalides including the ones bearing an ester group with the titanocene(II) species produced cyclopropanes in good yields. The reaction of dihalides possessing two secondary halogens proceeded stereoselectively to afford trans

Organolithium addition to styrene and styrene derivatives: Scope and limitations

Styrene and a range of aryl-substituted styrene derivatives are shown to undergo efficient carbolithiation-trapping reactions in diethyl ether at -78 to -25 °C. The reactivities of different types of organolithium reagents were found to be: tertiary, secondary > primary; ? alkenyl, methyl, phenyl. Electron donating groups (e.g. methoxy and dialkylamino) at the ortho- or para- positions of the benzene ring deactivate the double bond towards organolithium addition, but their reactions with butyllithium can be facilitated by using TMEDA as co-solvent. 2-Benzyloxystyrene and 2-allyloxystyrene undergo efficient carbolithiation at -78 °C, but at room temperature alkyl transfer occurs, generating the corresponding alkylated phenol. 2-Vinylnaphthalene also undergoes carbolithiation-carboxylation in reasonable yield.