Propargylation amines

In the flask were placed 10.0 g of the propargylic amine (see Chapter lIII-5, Exp. 1). The air in the flask was replaced with nitrogen and a solution of 0.01 mol of KO-tert.-Ci,H,3 in 10 g of THF (free from hydroperoxide) was added. The mixture was warmed at about 40 C. A weakly exothermic reaction was observed and the temperature rose to about 45°C. After 1-2 min the gel originally present, had disappeared almost completely and a brown solution had formed. The refractive index of the solution (note 1) was measured after intervals of about 2 min. After the... 

Recently, it has been reported that l,3-dithiole-2-thione (12) reacts with primary amine to give the corresponding thiourea and A-4-thia2oline-2-thione (Scheme 5) (14). 5-Methylenethiazolidine-2-thione (13) obtained from the reaction of propargyl amine and carbon disulfide... 

Fischer, C. 8c Carreira, E.M. (2004) Mgl2 an Additive in Ir(I)-Catalyzed Addition ofSUylacetylenes to Imines Expeditions Synthesis of Propargylic Amines. Synthesis, 9, 1497-1503. 

Table 2. Silylcarbocyclization of propargyl alcohols and propargyl amines with Rh catalysts .

Recently, the solvolyses of l-chloro-l,3,3-triarylallenes 10 (andof 1-butyl-3,3-diphenyl-allenyl chloride) were carried out in the presence of thiocyanate and o-ethyl dithiocar-bonate anions as nucleophiles and found to give the corresponding allenyl derivatives 11 and 12 in good yield (equation 3)18. However, when potassium cyanate was used as a nucleophile, the cyanate ion attacked at the /-position to give the propargyl amines 14 after decarboxylation of the unstable intermediate 13 (equation 4). 

Tandem Sonogashira reactions starting with iodopyrrole 122 have furnished the dipyrrolylacetylene 124, and dimerization of 123 gives 125 [86], The Sonogashira coupling has also been reported for enol triflate 55 reacting with an /V-protected propargyl amine [81]. 

The Stille adduct of 2-bromothiophene and l-ethoxy-2-tributyl-n-stannylethene or 1-ethoxy-l-tri-n-butylstannylethene is a masked thienyl aldehyde or a masked ketone, respectively [77-80]. Vinylstannane 93, derived exclusively as the -isomer from hydrostannation of bis(trimethyl-silyl)propargyl amine (92), was coupled with 2-bromothiophene to form ( )-cinnamyl amine 94 upon acidic hydrolysis [81, 82], In another case, stereoisomerically pure phenyl ( )-2-tributylstannyl-2-alkenoate 95, arising from Pd-mediated hydrostannation of phenyl ( )-2-alkynoate, was joined with 2-iodothiophene to deliver the stereodefmed trisubstituted a,p-unsaturated ester 96 [83, 84],... 

C1 Trityl Chloride resin (17.33 g, NovaBiochem, Lot A20915, 200 - 400 mesh, 1 % DVB, 1.33 mmol / g, 23.0 mmol) was placed in a 500-mL round-bottom flask. /V,/V-Dimcthylformamide (200 mL) was added, which caused the resin to swell this suspension was gently stirred by a magnetic stir bar. Propargyl amine (10 g,... 

Trace amounts of unreacted propargyl amine were observed to be the lone impurity in some reactions. 

A number of alkyl-substituted propargylic amines have been isomerized in that way [186, 191, 248-251], occasionally also providing alkynylamines as side-products. Compound 106 shows a recent example of a selective isomerization [252] (Scheme 1.46). 

Allenyl bromide accepts the nucleophilic attack of amines or potassium thio-acetate leading to propargylic amines or thioesters via the alkenylidenecarbene 132 or zwitterion intermediate 133 [66],... 

In the presence of K2C03, the reaction afforded propargylic amine 137 together with the corresponding iminium triflate 136 [67]. 

Secondary propargylic amines 284 (R = Pr, t-Bu, C5H11, C6H13 or C7H15) rearrange to the enamines 285 and thence to the imines 286 in the presence of potassium r-butoxide313. 

Scheme 3.17. Synthesis of functionalized a-amino acids by silylcupration [72a] or stannylcupration [81c] of chiral propargyl amines (Boc = t-butoxycarbonyl TFA = trifluoroacetic acid).

From unsymmetrical propargyl alcohol and propargyl amine derivatives as coupling partners of diynes, the corresponding axially chiral alcohols and amines were obtained in almost perfect diastereo- and enantioselectivities (Scheme 11.13). 

This unusual reactivity was subsequently extended to a broad variety of allylic and propargylic amines, in combination with other ruthenium(II) metal fragments, allowing the isolation of aminoaUenylidene complexes 33-35 [47 9] (Fig. 6). In addition, the S3mthesis of the thio-allenylidene [44] and seleno-aUenylidene [50] derivatives 36 from the in situ generated butatrienylidene tra s-[RuCl (=C=C=C=CH2)(L2)2] (L2 = dppm, dppe) and the corresponding aUyl sulfides... 

Scheme 5.4. Asymmetric synthesis of propargyl amines via the CDC reactions.

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