Pd(II)-Catalyzed C═C Bond Cleavage by a Formal Group-Exchange Reaction

Abstract

A chelation-assisted palladium-catalyzed CC bond cleavage of α, β-unsaturated ketone to form alkenyl nitrile in the presence of nitrile is disclosed on the basis of a formal group-exchange reaction formulated as C1C2 + C3 → C1C3 + C2, differing from normal alkene oxidative cleavage and metathesis type. The isolated key active Pd­(II) complex as well as deuterium-labeled experiment revealed the necessity of the chelation group, and a plausible catalytic pathway was proposed.

MOF-based Pd catalysts: a controllable and efficient platform towards cyclization reactions of isonitriles

“…[15][16][17] Generally, the state transformation of catalysts between Pd(II) and Pd(0) species serves as the dominating step for an efficient catalytic turnover in most Pd-catalyzed reactions. For example, (i) the reoxidation of Pd(0) to generate Pd(II) species in oxidative reactions; [18][19][20] (ii) the oxidation-addition process of Pd(0) to form Pd(II) species in coupling reactions; [21][22][23] (iii) Pd(II)-catalyzed reactions involving the use of a ligand, base or other additives, 24,25 which might lead to catalyst deactivation and thus impact the efficiency of the catalytic process. 26 However, the transformations of the valence and aggregation state of Pd species easily deactivate the catalyst (Scheme 1a).…”

Fluorapatite‐Supported Palladium Catalyst for the Synthesis of Alkenyl Nitriles

“…The traditional C=C bond cleavage reaction can be divided into two types: oxidative cleavage and alkene metathesis. [1] Nitriles are one of the fundamental constituents in biologically active compounds, functional materials, synthetic intermediates, and natural products. [2] CN group can be applied as a precursor to transform into various functional groups, such as amines, aldehydes, amides, amidines, tetrazoles, and carboxylic acids.…”

“…[3,[7][8][9][10] The main pathway would be direct alkene cyanation which directly introduces a cyano group into a double bond through a carbon-carbon coupling reaction. [1] Cinnamonitriles are synthetic intermediates, and various methods are used for their syntheses, such as reaction of cinnamaldehyde with dimethylsulfur diimides, treatment of acid chlorides with sulphonamides, and Wittig-Horner reaction of (EtO) 2 POCH 2 CN with aldehydes. Various catalysts and synthesis procedures are reported for cinnamonitriles in the last decade.…”

Iodine-Mediated C═C Double Bond Cleavage toward Pyrido[2,1-b]quinazolinones

“…Cleavage of carbon–carbon bonds is a challenging and fundamental transformation in the synthesis of complex organic compounds, and cleavage reactions of CC double bonds in particular have attracted considerable attention. In addition to the wide application of the olefin metathesis reactions in both laboratory synthesis and industrial production, CC bond cleavage reactions have been successfully employed to access carbonyl- and nitrogen-containing compounds . However, many such transformations use transition metals, and less attention has been paid to CC bond cleavage under transition-metal-free conditions. ,, In 2013, the Jiao group devised a TEMPO-catalyzed aerobic CC bond cleavage of hydrocarbons leading to N- and O-containing products .…”