Palladium-Catalyzed Hydrogenolysis of Allylic and Propargylic Compounds with Various Hydrides

Dawn of organopalladium chemistry in the early 1960s and a retrospective overview of the research on palladium-catalyzed reactions

“…67 The reaction of allyl cyanoacetate 143 provided lactone 145 in 56% yield as a main product and alcohol Although the hydrogenolysis of allylic compounds to produce alkenes is a simple reaction, it has wide application when proceeding regio-and stereosectively. 72 Several hydride sources act as nucleophiles, attacking p-allylpalladium intermediates, and resulting in the hydrogenolysis to afford alkenes. The first report on the palladium-catalyzed hydrogenolysis of allylic compounds with formic acid to give a mixture of alkene isomers was given by Hey and Arpe more than 40 years ago.…”

8.26 Reduction of Saturated Alkyl Halides to Alkanes

“…16 A variety of hydrogen sources can be used to this end. 17 In Scheme 8, a mixture of isomeric bromides was reduced using catalytic homogeneous palladium and stoichiometric tributyltin hydride. Silica gel doped with K 2 CO 3 was used to remove tin residues from the mixture.…”

Reactivity versus Stability of Oxiranes under Palladium‐Catalyzed Reductive Conditions

“…[131] The hydrogenolysis of the epoxide can be followed by the over-reduction of the C=C bond yielding the saturated alcohol and/or its migration leading to the ketone [Equation (62)]. [132] Through the various 4,5-epoxy-2-alkenoates reduced by Shimizu, Tsuji, and coworkers, [130,[133][134][135][136] the influence of the experimental conditions on the selectivity was particularly studied by using (E)-ethyl trans-4,5-epoxy-4-methyl-5-phenyl-2-pentenoate as the substrate. [130] The catalyst induces the formation of cationic η 3 -allylpalladium complex 14A, which leads to various compounds (Scheme 15) with a selectivity depending on the nature of the ligand, Pd/L ratio (Table 11), and solvent.…”