Propargylamines, catalytic

Reaction with Propargyl Halides. The indium-mediated coupling of propargyl bromide with a variety of imines and imine oxides afforded homo-propargylamine derivatives in aqueous media under mild conditions.78 Propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(O) complex and indium(I) iodide in aqueous media was also studied (Eq.11.47).79... 

The scope of the Cu-catalyzed cycloaddition between propargylamines and electron-deficient olefins in the presence of catalytic amounts of a copper salt was subsequently expanded to a one-pot, three-component coupling strategy involving phenols as third components [65]. In this case, reactive Michael acceptors such as ethyl 2-aryl- or alkylsulfonyl cinnamates 57 are involved in the process. This sequence leading to 3(4)-phenoxymethyl pyrrolidines 60 and their isomeric pyrrolidines 61 comprises of the relay process of... 

The reaction was successfully extended to the hydroformylation of propargyl-type alcohols [154] and propargylamine [155], the silylative cyclocarbonylation of alkynes [156], silylcarbocyclization of alkenynes and diynes [157-160], and other transformations of C=C bonds in the presence of HSiRa and CO (e. g., [161]). A generalized catalytic cycle for the silylformylation of 1-alkynes catalyzed by rhodium-cobalt clusters is illustrated in Scheme 6. 

Even formation of an acetyhde which adds to ketones and aldehydes can be promoted by a catalytic amount of cesium hydroxide (Scheme 2.36). Propargylamine, which has an acidic proton, is deprotonated elFiciently to form an acetylide. This adds to aldehydes in good yield without forming an imine (Scheme 2.37) [52]. 

The hyfroformylation of propargylamines 202 in the presence of the classical catalytic system [Rh(OAc)2]2/PPh3 gives 2,4-disubstituted pyrroles 204 in excellent yields, through consecutive hydroformylation, cyclization and double bond isomerization [116, 117]. 

The Cu(I)-catalyzed direct addition of terminal alkynes to imines generated in situ from aldehydes and amines affords synthetically useful propargylamines. This metal-catalyzed carbon-carbon bond formation is best performed in toluene but water is also a convenient solvent. While the achiral process is mediated by the bimetallic catalytic system RuCls/CuBr, CuOTf in conjunction with chiral bis(oxazolines) has been found optimal for enantioselective additions (eq 119). 

Corma A, Navas J, Sabater Ml (2012) Coupling of two multistep catalytic cycles for the one-pot synthesis of propargylamines from alcohols and primary amines on a nanoparticulated gold catalyst. Chem-Eur J 18(44) 14150-14156... 

The enantioselective, catalytic, three-component Mannich-acetylene reaction is the most direct and economical way to afford chiral nitrogen-containing building blocks. In this field, a great development has been accomplished in the use of different chiral molecules as ligands for several copper(l) salts as catalyst for the synthesis of chiral propargylamines 39. Thus, the addition of phenylacetylene (22a, = Ph) to... 

Table 3.5 Catalytic hydrogenation of propargylamines with magnetic Pd nanocatalyst...

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