DFT studies on the palladium-catalyzed dearomatization reaction between naphthalene allyl chloride and allyltributylstannane.

The Pd-catalyzed dearomatization of naphthalene allyl chloride with allyltributylstannane has been investigated using density functional theory (DFT) calculations at the B3LYP level. The calculations indicate that the (ŋ(1)-allyl)(ŋ(3)-allyl)Pd(PH3) complex is responsible for the formation of ortho-dearomatized product. Moreover it is easy to produce the ortho-dearomatized product when reductive elimination starts from (ŋ(3)-allylnaphthalene)(ŋ(1)-allyl)Pd complex 7, while it is easy to form the para-dearomatized product when reductive elimination starts from (ŋ(3)-allylnaphthalene)(ŋ(1)-allyl)Pd complex 9. The Stille coupling products can't be produced due to high reaction energy barrier. Graphical Abstract Two mechanisms of dearomatization are investigated by DFT, and (ŋ(1)-allyl)(ŋ(3)-allyl)Pd(PH3) complexes are the main intermediates for ortho-dearomatized product.