title: Practical Stannylation of Allyl Acetates Catalyzed by Nickel with Bu3 SnOMe.
abstract: A practical and scalable nickel-catalyzed allylic stannylation of allyl acetates with Bu3 SnOMe is described. A variety of acyclic and cyclic allyl acetates, even with base-sensitive moieties, undergoes the stannylation by using NiBr2 /4,4'-di-tert-butylbipyridine (dtbpy)/Mn catalyst system to afford highly functionalized allyl stannanes with excellent regioselectivity and yields. Furthermore, the scope of protocol is also extended by the reaction of propargyl acetates, giving rise to propargyl or allenyl stannanes. Additionally, a unique diastereoselectivity using the nickel catalyst different from the palladium was demonstrated for the stannylation of cyclic allyl acetates. In the reaction, inexpensive and stable nickel complexes, abundant reductant (Mn), and atom-economical stannyl source were used.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi, Hiroshima, 739-8527, Japan. kkome@hiroshima-u.ac.jp.
authors.forename: Kimihiro
authors.initials: K
authors.lastname: Komeyama
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi, Hiroshima, 739-8527, Japan.
authors.forename: Yuuhei
authors.initials: Y
authors.lastname: Itai
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi, Hiroshima, 739-8527, Japan.
authors.forename: Ken
authors.initials: K
authors.lastname: Takaki
keywords: allyl stannanes; nickel; stannyl alkoxide; stannylation; synthetic method