61862-37-1Relevant articles and documents
A general nickel-catalyzed hydroamination of 1,3-dienes by alkylamines: Catalyst selection, scope, and mechanism
Pawlas, Jan,Nakao, Yoshiaki,Kawatsura, Motoi,Hartwig, John F.
, p. 3669 - 3679 (2007/10/03)
A simple colorimetric assay of various transition-metal catalysts showed that the combination of DPPF, Ni(COD)2, and acid is a highly active catalyst system for the hydroamination of dienes by alkylamines to form allylic amines. The scope of the reaction is broad; various primary and secondary alkylamines react with 1,3-dienes in the presence of these catalysts. Detailed mechanistic studies revealed the individual steps involved in the catalytic process. These studies uncovered unexpected thermodynamics for the addition of amines to π-allyl nickel complexes: instead of the thermodynamics favoring the reaction of a nickel allyl with an amine to form an allylic amine, the thermodynamics favored reaction of a nickel(0) complex with allylic amine in the presence of acid to form a Ni(II) allyl. The realization of these thermodynamics led us to the discovery that nickel and some palladium complexes in the presence or absence of acid catalyze the exchange of the amino groups of allylic amines with free amines. This exchange process was used to reveal the relative thermodynamic stabilities of various allylic amines. In addition, this exchange reaction leads to racemization of allylic amines. Therefore, the relative rate for C-N bond formation and cleavage influences the enantioselectivity of diene hydroaminations.
Palladium-Catalyzed Substitutions of Allylic Nitro Compounds. Regiochemistry
Tamura, Rui,Kai, Yoshiki,Kakihana, Masato,Hayashi, Koji,Tsuji, Masanori,et al.
, p. 4375 - 4385 (2007/10/02)
Primary, secondary, and tertiary allylic nitro compounds underwent Pd(0)-catalyzed allylic substitution by stabilized carboanions, secondary amines, and benzenesulfinate ion (PhSO2-). α,β-disubstituted α-nitro olefins also behaved as allylic nitro compounds, via base-catalyzed vinyl -> allyl rearrangement, and underwent allylic substitution by secondary amines and PhSO2-.The regiochemistry of these substitutions was dependent on the structure of the allylic nitro compound amd on the steric bulk of the nucleophile.Generally, substitution occurred at the lesshindered or least substituted site.In some cases added or generated NaNO2 affected the regioselectivity of the allylic substitution of allylic nitro compounds and some allylic acetates by PhSO2-.Under these conditions, the more sterically hindered allylic sulfones were formed.
