Hydroamination of 1,1-dimethylallene with primary aryl amines under mild conditions: An atom-economical route to N-(1,1-dimethyl-2-propenyl)-anilines

Transition‐Metal‐Catalyzed Hydroamination Reactions

“…This new catalyst system can mediate the hydroamination of 1,1-disubstituted allenes with a range of cyclic and acyclic dialkylsecondary amines as well as some cyclic alkylarylamines [232]. Alternatively, the incorporation of bulky alkyl substituents on both the phosphorus and nitrogen moieties in the iminophosphine ligands has allowed for the regioselective synthesis of allylamines with a quaternary center adjacent to nitrogen (Scheme 15.45) [234]. This regioselectivity achieved with aniline as a substrate is in contrast to the results achieved with the secondary amines described earlier and most importantly, was used to advantage in the development of an acidcatalyzed aryl-amino Claisen rearrangement to make o-allyl-substituted aniline derivatives in a one-pot synthesis [234].…”

“…Alternatively, the incorporation of bulky alkyl substituents on both the phosphorus and nitrogen moieties in the iminophosphine ligands has allowed for the regioselective synthesis of allylamines with a quaternary center adjacent to nitrogen (Scheme 15.45) [234]. This regioselectivity achieved with aniline as a substrate is in contrast to the results achieved with the secondary amines described earlier and most importantly, was used to advantage in the development of an acidcatalyzed aryl-amino Claisen rearrangement to make o-allyl-substituted aniline derivatives in a one-pot synthesis [234]. In gold-catalyzed allene hydroamination, Bertrand has shown that the previously discussed cationic CAAC complexes for Au(I) ( [179], and with both primary and secondary amines [235].…”

Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride

“…To date, most of the studies have targeted complexes of the form [(3IP) Pd(allyl)][OTf] (Fig. 1A) since these species have proven to be very effective catalysts for the hydroamination of alkynes [38], 1,3-dienes [37,38], and allenes [36,37]. In addition to catalytic experiments, stoichiometric reactions have shown that the weakly bound imine nitrogen donor atom in the chloride complex, (3IP)PdCl 2 (Fig.…”

Gold(I)‐Catalyzed Stereoconvergent, Intermolecular Enantioselective Hydroamination of Allenes

“…[2] However, despite considerable efforts in this area, [1] effective intermolecular EHA processes are scarce, [3] and the intermolecular EHA of allenes remains unknown. [4,5] To circumvent this regiochemical bias, we envisioned the stereoconvergent, intermolecular EHA of chiral, racemic 1,3disubstutited allenes catalyzed by chiral bis(gold) phosphine complexes. [4,5] To circumvent this regiochemical bias, we envisioned the stereoconvergent, intermolecular EHA of chiral, racemic 1,3disubstutited allenes catalyzed by chiral bis(gold) phosphine complexes.…”

“…[4] One of the challenges associated with the intermolecular EHA of allenes is the regioselectivity of extant hydroamination catalysts, which form predominantly achiral products from electronically unbiased monosubstituted allenes. [4,5] To circumvent this regiochemical bias, we envisioned the stereoconvergent, intermolecular EHA of chiral, racemic 1,3disubstutited allenes catalyzed by chiral bis(gold) phosphine complexes. This approach builds upon our previous efforts in the area of gold-catalyzed allene hydroamination.…”