55169-03-4

Upstream product

• 920-39-8 isopropylmagnesium bromide 
• 14534-83-9 4-butyl-tri-N-methyl-anilinium; iodide 
• 185416-14-2 4-(1-butyl)phenylmagnesium bromide 
• 41492-05-1 p-bromobutylbenzene 
• 15499-27-1 4-n-butylchlorobenzene 
• 1888-75-1 isopropyllithium 
• 78575-06-1 1-(4-isopropyl-phenyl)-butan-1-one 
• 100532-13-6 1-(4-isopropyl-phenyl)-butan-1-ol 

Relevant academic research and scientific papers

Nickel-induced Conversion of Carbon-Nitrogen into Carbon-Carbon Bonds. One step Transformations of Aryl, Quaternary Ammonium Salts into Alkylarenes and Biaryls

Aryltrimethylammonium iodides are shown to undergo reaction with Grignard reagents under phosphinate-ligated, low-valent nickel catalysis with the formation of alkylarenes and biaryls.

Efficient Pd-Catalyzed Direct Coupling of Aryl Chlorides with Alkyllithium Reagents

Organolithium compounds are amongst the most important organometallic reagents and frequently used in difficult metallation reactions. However, their direct use in the formation of C?C bonds is less established. Although remarkable advances in the coupling of aryllithium compounds have been achieved, Csp2?Csp3 coupling reactions are very limited. Herein, we report the first general protocol for the coupling or aryl chlorides with alkyllithium reagents. Palladium catalysts based on ylide-substituted phosphines (YPhos) were found to be excellently suited for this transformation giving high selectivities at room temperature with a variety of aryl chlorides without the need for an additional transmetallation reagent. This is demonstrated in gram-scale synthesis including building blocks for materials chemistry and pharmaceutical industry. Furthermore, the direct coupling of aryllithiums as well as Grignard reagents with aryl chlorides was also easily accomplished at room temperature.

Facile Hydrogenolysis of C(sp3)–C(sp3) σ Bonds

The modification of benzylic quaternary, tertiary, and secondary carbon centers through palladium-catalyzed hydrogenolysis of C(sp3)–C(sp3) σ bonds is presented. When benzyl Meldrum's acid derivatives bearing quaternary benzylic centers are treated under mild hydrogenolysis conditions – palladium on carbon and atmospheric pressure of hydrogen – aromatics substituted with tertiary benzylic centers and Meldrum's acid are obtained with good to excellent yield. Analogously, substrates containing tertiary or secondary benzylic centers yield aromatics substituted with secondary benzylic centers or toluene derivatives, respectively. Furthermore, this strategy is used for the high yielding synthesis of diarylmethanes. The scope of the reductive dealkylation reaction is explored and the limitations with respect to steric and electronic factors are determined. A mechanistic analysis of the reaction is described that consisted of deuterium labelling experiments and hydrogenolysis of enantioenriched derivatives. The investigation shows that the C(sp3)–C(sp3) σ bond-cleaving events occur through a hybrid SN1/SN2 mechanism, in which the palladium center displaces a carbon-based leaving group, namely Meldrum's acid, with inversion of configuration, followed by reductive elimination of palladium to furnish a C?H bond. (Figure presented.).