Propargyl amines, synthesis

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. 

Shore G, Yoo W-J, Li C-J et al (2009) Propargyl amine synthesis catalysed by gold and copper thin films by using microwave-assisted continuous-flow organic synthesis (MACOS). ChemEur J 16 126-133... 

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).

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

Scheme 5.8. CuBr/PINAP-catalyzed asymmetric synthesis of propargyl amines.

D hooghe, M. Van Brabandt, W. De Kimpe, N. New Synthesis of Propargylic Amines from 2-(Bromomethyl)aziridines. Intermiediacy of 3-Bromoazetidinium Salts. /. Org. Chem. 2004, 69, 2703-2710. 

Imada, Y. Yuasa, M. Nakamura, I. Muraha-shi, S.-I. Copper(I)-catalyzed amination of pro-pargyl esters. Selective synthesis of propargyl-amines, l-alken-3-ylamines, and (Z)-allyl-amines./. Org. Chem. 1994, 59, 2282-2284. 

A similar synthesis has been described involving partial hydrogenation of the triple bond of a 1-silyl propargyl amine (see Section III.B.l.b). 

The reaction has been extensively used for the synthesis of a-amino acids (entries 3-5),559 //-/ -amino alcohols (entry 6),560 aminophenol (entry 7),561 optically active A-substituted glycines (entries 7 and 8),562 a-hydrazinocarboxylic acids (entry 9),563 A-sulfinyl and A-alkoxy-a-amino acids (entries 10 and ll),564 and propargyl amines (entry 12).565... 

It is worth mentioning the synthesis of cyclic a-methylene carbamates, which were also produced via Markovnikov intramolecular nucleophilic addition of O-car-bamates, generated in situ from a propargylic amine and CO2, in the presence of Ru(cod) (cot)/phosphine as catalyst precursor (cod cyclooctadiene cot cycloocta-triene) (Scheme 8.23) [75]. 

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 [47-49] (Fig. 6). In addition, the synthesis of the thio-allenylidene [44] and seleno-aUenylidene [50] derivatives 36 from the in situ generated butatrienylidene Zran.s - RuCI (=C=C=C=CH2)(L2)2] (L2 = dppm, dppe) and the corresponding aUyl sulfides... 

Propargyl amines are versatile intermediates in organic synthesis and an important structural motif in drug molecules. In addition, these p-amino-alkynes are also of importance as its two potential sites can be modified further to fit particular applications. 

Propargylic amines are high value building blocks in organic synthesis, and the corresponding stractural motif has been found in various natural products, and in compounds of pharmaceutical or phytoprotective relevance. They can be obtained by addition of alkynes to imines, bnt since imines are easily formed from aldehydes and amines. 

M. K. Patil, M. Keller, B. M. Reddy, P. Pale, J. Sommer, Copper-zeolites as green catalysts for multicomponent reactions an efficient and green synthesis of propargyl amines, Eur. J. Org. Chem., 2008, 26, 4440 445. 

Three-component synthesis of propargyl amines can be performed with copper(i) complexes or in... 

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