Cooperative Friedel−Crafts Catalysis in Heterobimetallic Regime:  Alkylation of Aromatics by π-Activated Alcohols

Abstract

The highly active Friedel-Crafts alkylation (FCA) catalyst, [Ir(COD)Cl(SnCl3)(SnCl4)(arene)]+Cl- (1-SnCl4), is easily generated in one-pot from [Ir(COD)Cl]2 or [Ir(COD)(mu-Cl)Cl(SnCl3)]2 (1) and SnCl4. The reaction of arenes, heteroarenes with benzyl, and allyl alcohols is promoted by 1-SnCl4 (1 mol %) with high turnover frequency. Kinetic evidence is presented to establish FCA pattern. From dual-catalyst combination studies varying the transition metal and main group metal partner, the efficiency of the present catalysts is attributed to the electrophilic "IrIII-SnIV" core.

Ir/Sn dual-reagent catalysis towards highly selective alkylation of arenes and heteroarenes with benzyl alcohols

“…21 A parallel investigation gave birth to new heterobimetallic transition metal-tin complexes. [22][23] Subsequently, the concept has been extended towards the activation of aldehydes, and ethers.…”

Steric Effect on the Catalytic Performance of the Selective Oxidation of Alcohols Over Novel Crystalline Mo–V–O Oxide

“…In a 24 h reaction, 32% conversion of benzyl alcohol was achieved with the 42% selectivity of benzaldehyde. The main products by the MoVO-AM catalyst were benzoic acid, benzyl benzoate and benzylated toluene [44,45], suggesting the over-oxidation of benzaldehyde and the alkylation occurred.…”

Microwave-assisted hydroarylation of styrenes catalysed by transition metal oxide nanoparticles supported on mesoporous aluminosilicates

“…Protocols have been developed using various transition-metal and acid catalysts [5,6]. The addition of olefins to acetophenones [7,8] and aromatic imines [9,10], alkene additions to arenes [2,4] and heterocyclic compounds [11,12] as well as the addition of aromatics to alkynes [13,14] or alcohols [15] are elegant examples of these types of transformation. In particular, the use of aromatic-derived alkenes has been found to be very useful and practical as the resulting diarylalkane block represents an important part in biologically active compounds and pharmaceuticals substrates that include haplopappin, phenprocoumone, papaverine, or afenopin ( Fig.…”

“…aluminosilicates) can be increased via incorporation of metal ions such as Cu II , Zn II , Fe III , etc., which causes the generation of highly active Lewis acid sites [21]. The combination of such active Lewis acid site along with the available Brönsted acid sites in metal-exchanged Al-SBA- 15 their pores/external surfaces and providing high local concentration [22,23]. Among these transition metals, iron NPs have attracted a great interest in the design of environmentally friendly and effective catalysts as alternative to traditionally employed noble metal catalysts in several catalytic reactions.…”