Gold(I)-Catalyzed Intramolecular Amination of Allylic Alcohols With Alkylamines

Abstract

A 1:1 mixture of (1)AuCl [1 = P(t-Bu)2o-biphenyl] and AgSbF6 catalyzes the intramolecular amination of allylic alcohols with alkylamines to form substituted pyrrolidine and piperidine derivatives. Gold(I)-catalyzed cyclization of (R,Z)-8-(N-benzylamino)-3-octen-2-ol (96% ee, 95% de) led to isolation of (R,E)-1-benzyl-2-(1-propenyl)piperidine in 99% yield with 96% ee, consistent with the net syn addition of the amine relative to the departing hydroxyl group.

Gold(I)-catalyzed synthesis of γ-vinylbutyrolactones by intramolecular oxaallylic alkylation with alcohols

“…This evidence is reasonably rationalized in terms of the high π-acidity and poor oxophilicity of the Au(I) species [37]. …”

“…The wide impact of functionalized γ-lactones on the synthesis of naturally occurring compounds [24–26] prompted us to optimize a direct synthesis of vinylbutyrolactones by direct gold activation of allylic alcohols [27–31] with esters [32–37]. …”

Gold(I)‐Catalyzed Enantioselective Intramolecular Dehydrative Amination of Allylic Alcohols with Carbamates

“…

The transition-metal-catalyzed enantioselective amination of allylic esters and carbonates represents one of the most wellestablished routes to chiral, nonracemic allylic amines. However, while the stereospecific amination of chiral secondary allylic alcohols has been demonstrated, [2][3][4] the enantioselective amination of allylic alcohols remains problematic. However, while the stereospecific amination of chiral secondary allylic alcohols has been demonstrated, [2][3][4] the enantioselective amination of allylic alcohols remains problematic.

…”

“…[6] Hartwig et al have reported the Ir I /BPh 3 -catalyzed enantioselective intermolecular amination of primary allylic alcohols with aromatic amines with up to 94 % ee, but this method was restricted to cinnamyl alcohols in the absence of a stoichiometric Lewis acid promoter. [4,10] Encouraged by the high efficiency and stereospecificity of this transformation and guided by both our previous work in the area of gold(I)catalyzed enantioselective allene hydroamination [11,12] and Bandinis recent demonstration of gold(I)-catalyzed enantioselective arylation [13] and alkoxylation [14] of allylic alcohols, [15] we targeted axially chiral bis(gold) complexes as catalysts for the intramolecular enantioselective amination of the ebenzylamino allylic alcohol (E)-1 a (Table 1). However, these methods were restricted to sulfonamide nucleophiles and high enantioselectivity was realized only for the formation of arene-fused nitrogen heterocycles.…”

“…[4,10] Encouraged by the high efficiency and stereospecificity of this transformation and guided by both our previous work in the area of gold(I)catalyzed enantioselective allene hydroamination [11,12] and Bandinis recent demonstration of gold(I)-catalyzed enantioselective arylation [13] and alkoxylation [14] of allylic alcohols, [15] we targeted axially chiral bis(gold) complexes as catalysts for the intramolecular enantioselective amination of the ebenzylamino allylic alcohol (E)-1 a (Table 1). [4,10] Encouraged by the high efficiency and stereospecificity of this transformation and guided by both our previous work in the area of gold(I)catalyzed enantioselective allene hydroamination [11,12] and Bandinis recent demonstration of gold(I)-catalyzed enantioselective arylation [13] and alkoxylation [14] of allylic alcohols, [15] we targeted axially chiral bis(gold) complexes as catalysts for the intramolecular enantioselective amination of the ebenzylamino allylic alcohol (E)-1 a (Table 1).…”