Mercury in organic chemistry. 14. A convenient regiospecific synthesis of .pi.-allylpalladium compounds via vinylmercurials

Palladium-Catalyzed, Asymmetric Hetero- and Carboannulation of Allenes Using Functionally-Substituted Aryl and Vinylic Iodides

“…To confirm this suspicion, we synthesized and isolated di-μ-chlorodi(η 3 -5-phenylnon-4-enyl)dipalladium(II) as a mixture of oil and crystals . Proton and 13 C NMR analysis of the viscous oil component showed a 1:1 mixture of syn-syn and syn-anti isomers, while the crystals were essentially pure syn-syn isomer.…”

“…Di-μ-chlorodi(η 3 -5-(2‘-hydroxymethylphenyl)non-4-enyl)dipalladium(II) has been prepared by the reaction of 2-(chloromercurio)benzyl alcohol, 4,5-nonadiene, and Li 2 PdCl 4 , but this π-allylpalladium compound rapidly decomposed at room temperature. Therefore, we were unable to attempt to correlate the ratio of syn-syn and syn-anti isomers to the ee of the annulation product ( E )-4- n -butylidene-3,4-dihydro-3- n -propyl-1 H -2-benzopyran.…”

Dilithium Tetrachloropalladate(II)

“…10 The analogous reaction of monocyclic alkenes affords either (π-allyl)palladium complexes or 1,4-dienes, depending on the reaction conditions employed (eq 3). 2 (π-Allyl)palladium complexes can be prepared by the reaction of Li 2 PdCl 4 with bicyclic alkenes, 11 dienes, 12 vinyl-and methylenecyclopropanes, 13 vinyl-and methylenecyclobutanes, 14 and dienolsilyl ethers.…”

New organometallic approaches to heterocycles

“…Larock and Mitchell (199) Trying to extend this reaction to larger ring lactones by the use of 6heptenoic acid or 10-undecenoic acid proved unsuccessful and led only to recovery of the starting acid.…”