Propargylamines, three component synthesis

A. Bisai, V. K. Singh, Org. Lett. 2006, 8, 2405-2408. Enantioselective one-pot three-component synthesis of propargylamines. 

S. Nakamura, M. Ohara, Y. Nakamura, N. Shibata, T. Toru, Chem.-Eur. J. 2010, 16, 2360-2362. Copper-catalyzed enantioselective three-component synthesis of optically active propargylamines from aldehydes, amines, and aliphatic alkynes. 

N. Gommermann, P. Knochel, Chem. Commun. 2005,4175-4177. 2-PhenaUyl as a versatile protecting group for the asymmetric one-pot three-component synthesis of propargylamines. 

Several new methods for the synthesis of the oxazole nucleus were published. A new consecutive three-component oxazole synthesis by an amidation-coupling-cycloisomerisation sequence was developed. The synthesis started from propargylamine 92 and acyl chlorides. To extend this process, a four component sequence involving a carbonylative arylation by substitution of one acyl chloride with an aryl iodide and a CO atmosphere was also performed <06CC4817>. 

A copper-catalyzed one-pot three-component atom-economical C-H functionalization process was used to form enantioenriched propargylamines. This protocol was also employed for the synthesis of the alkaloid (A)-(+)-coniine (Equation (196)).159 159a... 

Scheme 9.27. Enantioselective three-component reaction for the synthesis of propargylamines.

Other nucleophiles that have been used in this context are acetylides (alkynes). The addition of those to iminium cations generated in situ from aldehydes and secondary amines accomplishes a gold(III)-catalyzed three-component coupling for the synthesis of propargylamines, as can be observed in equation (124). The reactions are performed in water or in tetrahydrofuran (THF) when supported catalysts are employed.Chiral prolinol derivatives as... 

Gold nanoparticles on ZnO were used as a catalyst for the rapid one-pot three-component condensation of amines (106), aldehydes (107), and phenyl acetylene (20), affording the selective synthesis of propargylamines (108) at room temperature (Scheme 9.32) (Gonzalez-Bejar et al. 2013). Propargylic alcohols constitute important building blocks for many biologically active compounds and natural products. 

A -Coupling and Related Reactions Three-component coupling of aldehydes, alkynes, and amines (A -coupling) is a powerful methodology for the synthesis of propargylamines [88], which has been widely explored using Cu-, Ag-, or Au-based catalysts (see Section 3.4.2). 

M. Kidwai, V. Bansal, A. Kumar, S. Mozumdar, Green Chem. 2007, 9, 742-745. The first Au-nanoparticles catalyzed green synthesis of propargylamines via a three-component coupling reaction of aldehyde, alkyne and amine. 

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... 

Gommermann, N., Knochel, P. (2006). Practical highly enantioselective synthesis of propargylamines through a copper-catalyzed one-pot three-component condensation reaction. Chemistry - A European Journal, 12, 4380-4392. 

Akullian, L. C., Snapper, M. L., Hoveyda, A. H. (2003). Three-component enantioselec-tive synthesis of propargylamines through Zr-catalyzed additions of alkyl zinc reagents to alkynylimines. Angewandte Chemie International Edition, 42, 4244-4247. 

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