title: Efficient synthesis of tetradecafluoro-4-phenylheptan-4-ol by a Cannizzaro-type reaction and application of the alcohol as a bulky Martin ligand variant for a new anti-apicophilic phosphorane.
abstract: Alcohols 8 bearing two identical perfluoroalkyl groups were prepared by the reaction of the corresponding perfluoroalkyl phenyl ketones 7 with 0.5 equivalents of t-BuOK via Cannizzaro-type disproportionation. Utilizing the new bulky bidentate ligand with two n-C(3)F(7) groups generated from 8c, anti-apicophilic phosphorane 5a and its stable isomer 6a were synthesized. The crystal structures of 5a and 6a were slightly affected by the steric repulsion of heptafluoropropyl groups. Kinetic studies on the isomerization of 5a to 6a showed that the new ligand was effective for decreasing the isomerization rate compared with its C(2)F(5) analog 3a to about half.
authors.affiliation: The Key Laboratory for Special Functional Materials, Ministry of Education, Henan University, Kaifeng, Henan, 475-004, China. xdjiang@henu.edu.cn
authors.forename: Xin-Dong
authors.initials: XD
authors.lastname: Jiang
authors.forename: Shiro
authors.initials: S
authors.lastname: Matsukawa
authors.forename: Ken-Ichiro
authors.initials: K
authors.lastname: Kakuda
authors.forename: Yuta
authors.initials: Y
authors.lastname: Fukuzaki
authors.forename: Wei-Li
authors.initials: WL
authors.lastname: Zhao
authors.forename: Lin-Song
authors.initials: LS
authors.lastname: Li
authors.forename: Huai-Bin
authors.initials: HB
authors.lastname: Shen
authors.forename: Satoshi
authors.initials: S
authors.lastname: Kojima
authors.forename: Yohsuke
authors.initials: Y
authors.lastname: Yamamoto
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry*; D006536:Heptanes / Q000138:chemical synthesis* / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D010753:Phosphoranes / Q000737:chemistry*
chemical_list: D000438:Alcohols; D006536:Heptanes; D008024:Ligands; D010753:Phosphoranes; C555575:tetradecafluoro-4-phenylheptan-4-ol