title: DFT studies on the palladium-catalyzed dearomatization reaction between naphthalene allyl chloride and allyltributylstannane.
abstract: 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.
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Cao
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China. tiandx@dlut.edu.cn.
authors.forename: Dongxu
authors.initials: D
authors.lastname: Tian
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China.
authors.forename: Dongxue
authors.initials: D
authors.lastname: Han
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D008956:Models, Chemical; D008958:Models, Molecular; D009281:Naphthalenes / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D017971:Tin Compounds / Q000737:chemistry*
chemical_list: D000498:Allyl Compounds; D009281:Naphthalenes; D017971:Tin Compounds; C031721:naphthalene; C031525:stannane; D010165:Palladium; C023698:allyl chloride
keywords: DFT; Dearomatization; NBO; Propenylnaphthalene