Terpenylammonium salts in Pd(dba)2 catalyzed allylic alkylation and in stoichiometric reactions with dibenzylideneacetone-palladium (0) complexes

Authors：Petrushkina E.A.^*; Nikolaev S.E.; Khomishin D.V.; Strelkova T.V.; Kononova E.G.; Mysova N.E.; Starikova Z.A.; Dolgushin F.M.

Source：Journal of Organometallic Chemistry, 2020, 922: 121373.

DOI：10.1016/j.jorganchem.2020.121373

• Allylic alkylation
• Di-μ-iodobis[(1,2,3-η)-2,7-dimethyl-2,7-and 2,6-octadienyl]dipalladium
• Terpenylammonium salts

Allyl alkylation of diethylmalonate with N-(2,7-dimethyl-2,7-octadien-1-yl)dialkylammonium iodide salts catalyzed by Pd (dba)2 without a phosphorus ligand and in the presence of NaH occurred with the predominant formation of a normal substitution product of SN2 type. A mixture of N-(2,7-dimethyl-2,7-octadien-1-yl)dialkylammonium iodide and N-(2,7-dimethyl-2,6-octadien-1-yl)dialkylammonium iodide yields a mixture of the corresponding malonates and di-μ-iodobis [(1,2,3-η)-2,7-dimethyl- 2,6-octadienyl]dipalladium. N-(2,7-dimethyl-2,7-octadien-1-yl)dialkylammonium iodide salts in reactions with both Pd (dba)2 and Pd2 (dba)3⋅CHCl3 yields only di-μ-iodobis [(1,2,3-η)-2,7-dimethyl- 2,7-octadienyl]dipalladium.