85100-62-5

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• 7335-27-5 ethyl 4-chlorobenzoate 
• 34219-54-0 n-butylzinc iodide 
• 69190-62-1 pinacol butylboronate 
• 109-72-8 n-butyllithium 
• 5798-75-4 Ethyl 4-bromobenzoate 
• 693-04-9 butyl magnesium bromide 
• 125261-30-5 p-(ethoxycarbonyl)phenyl triflate 
• 51934-41-9 4-iodobenzoic acid ethyl ester 
• 1286990-00-8 ethyl 4-((phenylsulfonyl)oxy)benzoate 
• 64-17-5 ethanol 
• 28788-62-7 4-butylbenzoyl chloride 
• 693-03-8 n-butyl magnesium bromide 
• 124915-06-6 ethyl 4-(N,N,N-trimethylammonium)-1-benzoate triflate 
• 3692-81-7 tri-n-butylbismuthine 

Relevant academic research and scientific papers

Scalable Negishi Coupling between Organozinc Compounds and (Hetero)Aryl Bromides under Aerobic Conditions when using Bulk Water or Deep Eutectic Solvents with no Additional Ligands

Pd-catalyzed Negishi cross-coupling reactions between organozinc compounds and (hetero)aryl bromides have been reported when using bulk water as the reaction medium in the presence of NaCl or the biodegradable choline chloride/urea eutectic mixture. Both C(sp3)-C(sp2) and C(sp2)-C(sp2) couplings have been found to proceed smoothly, with high chemoselectivity, under mild conditions (room temperature or 60 °C) in air, and in competition with protonolysis. Additional benefits include very short reaction times (20 s), good to excellent yields (up to 98 %), wide substrate scope, and the tolerance of a variety of functional groups. The proposed novel protocol is scalable, and the practicability of the method is further highlighted by an easy recycling of both the catalyst and the eutectic mixture or water.

Gram-Scale, Cheap, and Eco-Friendly Iron-Catalyzed Cross-Coupling between Alkyl Grignard Reagents and Alkenyl or Aryl Halides

A new robust methodology for gram-scale iron-catalyzed cross-coupling between alkyl Grignard reagents and alkenyl or aryl halides is developed. This method does not require toxic additives such as NMP or expensive ligands. Its efficiency relies on the use of simple alkoxide magnesium salts as additives. On the basis of these results, a new procedure for one-pot synthesis of substituted benzamides from chloroesters is also proposed.

Single-Electron-Transfer-Induced Coupling of Alkylzinc Reagents with Aryl Iodides

Alkylzinc reagents prepared from an alkyllithium and zinc iodide were found to undergo coupling with aryl and alkenyl iodides in the presence of LiI in a mixed solvent consisting of THF and diglyme (1:1). Alkyllithiums, prepared by halogen–lithium exchange between an alkyl iodide and tert-butyllithium, are also converted to alkylarenes through alkylzinc reagents.

Catalyst activation, deactivation, and degradation in palladium-mediated negishi cross-coupling reactions

Pd-mediated Negishi cross-coupling reactions were studied by a combination of kinetic measurements, electrospray-ionization (ESI) mass spectrometry, 31P NMR and UV/Vis spectroscopy. The kinetic measurements point to a rate-determining oxidative addition. Surprisingly, this step seems to involve not only the Pd catalyst and the aryl halide substrate, but also the organozinc reagent. In this context, the ESI-mass spectrometric observation of heterobimetallic Pd-Zn complexes [L2PdZnR]+ (L=S-PHOS, R=Bu, Ph, Bn) is particularly revealing. The inferred presence of these and related neutral complexes with a direct Pd-Zn interaction in solution explains how the organozinc reagent can modulate the reactivity of the Pd catalyst. Previous theoretical calculations by Gonzlez-Prez et al. (Organometallics 2012, 31, 2053) suggest that the complexation by the organozinc reagent lowers the activity of the Pd catalyst. Presumably, a similar effect also causes the rate decrease observed upon addition of ZnBr2. In contrast, added LiBr apparently counteracts the formation of Pd-Zn complexes and restores the high activity of the Pd catalyst. At longer reaction times, deactivation processes due to degradation of the S-PHOS ligand and aggregation of the Pd catalyst come into play, thus further contributing to the appreciable complexity of the title reaction. Catalytic complexity: The Pd catalyst used in Negishi cross-coupling reactions shows an unexpected heterogeneity and complexity. Among the various species observed in solution, heterobimetallic Pd-Zn complexes are of particular interest (see figure). These species also seem key to understanding the kinetics of Negishi cross-coupling reactions. S-PHOS=2-dicyclohexylphosphino-2,6-dimethoxybiphenyl.

Acid Chloride Synthesis by the Palladium-Catalyzed Chlorocarbonylation of Aryl Bromides

We report a palladium-catalyzed method to synthesize acid chlorides by the chlorocarbonylation of aryl bromides. Mechanistic studies suggest the combination of sterically encumbered PtBu3 and CO coordination to palladium can rapidly equilibrate the oxidative addition/reductive elimination of carbon-halogen bonds. This provides a useful method to assemble highly reactive acid chlorides from stable and available reagents, and can be coupled with subsequent nucleophilic reactions to generate new classes of carbonylated products. The Good, the Bad and the Bulky! By employing a sterically encumbered phosphine ligand, tri-tert-butyl phosphine, under palladium catalysis inert aryl bromides are chlorocarbonylated to create reactive acid chlorides by reversible carbon-halogen bond reductive elimination. This general platform allows for an expanded scope of the Heck carbonylation reaction to include previously incompatible nucleophiles.

Iron-catalyzed cross-coupling of aryltrimethylammonium triflates and alkyl Grignard reagents

Fe(acac)3 effectively catalyzes reaction of aryltrimethylammonium triflates with β-hydrogen-containing primary or secondary alkyl Grignard reagents in a mixed solvent of THF and NMP at room temperature. A series of functional groups are tolerated under the reaction conditions.

Iron thiolate complexes: Efficient catalysts for coupling alkenyl halides with alkyl grignard reagents

Ironing out the kinks: Efficient new catalytic systems based on iron thiolates are described for the iron-catalyzed cross-coupling of alkyl Grignard reagents with alkenyl halides (see scheme). The reaction is highly chemo- and stereoselective. With this new procedure, the use of N-methylpyrrolidone as a co-solvent is no longer required. Copyright

Csp3-Csp2 palladium-catalyzed cross-coupling reaction of trialkylbismuth reagents with aryl, heteroaryl, and vinyl halides and triflates

The palladium-catalyzed cross-coupling reaction of trialkylbismuth reagents with aryl and heteroaryl halides and triflates is reported. Moderate to good yields were obtained for the transfer of primary alkyl groups. The reaction tolerates numerous functional groups on the electrophilic and nucleophilic partners. The cross-coupling of -bromostyrene with tris(1,3-dioxan-2-ylethyl) bismuth is also reported. Georg Thieme Verlag Stuttgart - New York.

Air-stable secondary phosphine oxide or chloride (Pre)ligands for cross-couplings of unactivated alkyl chlorides

In situ generated and crystallographically well-defined, isolated palladium complexes derived from seven novel air-stable secondary phosphine oxides or chlorides enabled challenging Kumada-Corriu cross-couplings of unactivated alkyl chlorides bearing β-hy

Suzuki-Miyaura cross-coupling of lithium n-alkylborates

The palladium-catalyzed cross-coupling of lithium n-alkylborates, generated in situ via addition of sec-butyl lithium to boronate esters, proceeds in moderate to good yields with a wide variety of electrophiles.