1443414-02-5Relevant articles and documents
A Radical Pathway for Direct Substitution of Benzyl Alcohols with Water-Soluble Copper Catalyst in Water
Hikawa, Hidemasa,Mori, Yuki,Kikkawa, Shoko,Azumaya, Isao
, p. 765 - 773 (2016)
We have developed a novel strategy for the direct substitution of benzyl alcohols with anthranilic acids using water-soluble copper catalysts through a radical pathway in water, which offers efficient and environmentally friendly N-, S-, and C-benzylations under neutral conditions. Radical scavengers strongly inhibited the benzylation. Radical clock experiments using α-cyclopropylbenzyl alcohol were conducted to observe the rapid isomerization of the cyclopropylmethyl radical to the allylmethyl radical. Hammett plots could be fitted to a two-parameter Hammett relationship containing both radical and polar contributions [log (kX/kH)=-1.24 σ.-0.38 σ, R2=0.99]. The relative parameter ρ./ρ of 3.3 suggested that these reactions involved a strong radical character with minor polar influence at the transition state.
Chemoselective benzylation of unprotected anthranilic acids with benzhydryl alcohols by water-soluble Au(III)/TPPMS in water
Hikawa, Hidemasa,Suzuki, Hideharu,Yokoyama, Yuusaku,Azumaya, Isao
, p. 6714 - 6720 (2013/07/26)
A novel and efficient method for the benzylation of unprotected anthranilic acids with benzhydryl alcohols using water-soluble Au(III)/TPPMS in water is developed. Water plays an important role in our catalytic system. This new protocol could be used for not only N-benzylation, but also chemoselective C-benzylation by the Friedel-Crafts reaction.
