206768-81-2Relevant articles and documents
The First Catalytic Asymmetric Allylation of Imines with the Tetraallylsilane-TBAF-MeOH System, Using the Chiral Bis-π-allylpalladium Complex
Fernandes, Rodney A.,Yamamoto, Yoshinori
, p. 735 - 738 (2004)
The asymmetric allylation of imines with use of catalytic transition metals with chiral ligands should be a new frontier of the enantioselective C-C bond formation. So far allyltrimethylsilane, allyltrichlorosilane, and allyltrimethoxysilane have been commonly employed with use of either silane activators or dual silane-imine activators. However, tetraallylsilane is untouched in the allylation of aldimines. The first allylation of aldimines with the tetraallylsilane-TBAF-MeOH system with use of the bis-π -allylpalladium catalyst under catalytic, non-Lewis acid, essentially neutral and very mild reaction conditions has been achieved. The reaction is triggered by dual activation/promotion by TBAF and MeOH in which the fluoride anion activates the C-Si bond cleavage and MeOH promotes the facile protonation of intermediate palladium amide. Thus, the synthesis of chiral homoallylamines is achieved in a shorter reaction time and higher yields and enantioselectivities through an efficient, general, and reproducible allylation protocol for imines.
Preparation and application of a polymer-supported chiral π-allylpalladium catalyst for the allylation of imines
Bao, Ming,Nakamura, Hiroyuki,Yamamoto, Yoshinori
, p. 131 - 134 (2000)
The polymer-supported chiral π-allylpalladium catalyst 8 was applied to the asymmetric allylation reaction of imines 9 with allyltributylstannane. The catalyst was very stable and could be reused several times with high catalytic activity, although the enantioselectivity was not necessarily high.
Menthane-Based Chloride-Bridged η3-Bis-π-Allylpalladium Chloride Dimers: Catalytic Asymmetric Allylation of Imines
Jha, Amit K.,Fernandes, Rodney A.
, p. 2857 - 2863 (2019/05/15)
Menthane-based η3-bis-π-allylpalladium chloride dimer complexes have been prepared for the first time. They exist as dimeric η3-bis-π-allylpalladium with four chloride bridges. The complexes catalyze the asymmetric allylation of vari
Development of the first menthane-based chiral bis(π-allylpalladium) catalysis: Asymmetric allylation of imines
Fernandes, Rodney A.,Chaudhari, Dipali A.
experimental part, p. 1945 - 1952 (2012/05/20)
A new ethylidene menthane-based chiral π-allylpalladium complex catalyzes the asymmetric allylation of various imines with allyltributylstannane and 1 equiv. of water to give chiral homoallylamines in good yields and enantioselectivities. The reaction was carried out essentially under neutral conditions and displayed a good transfer of chiral information from the menthane skeleton through the formation of a bis(π-allylpalladium) species. This is the first example of menthane-based chiral bis(π-allylpalladium) catalysis. A menthane-based chiral π-allylpalladium-catalyzed asymmetric allylation of various imines has been developed giving chiral homoallylamines in good yields and enantioselectivities. The reaction displays a good transfer of chiral information from the menthane skeleton through the formation of a bis(π-allylpalladium) complex. Copyright
