Synthesis of propargylamines

Similarly, an efficient procedure of general applicability was described for the synthesis of propargylamines by copper(I)-catalyzed amination of bromoal-lenes [75], It should be mentioned that by use of an enantioenriched allene 142 (R1 = nPr, R2 = Me), the optical purity was completely transferred to alkyne 143 (R3 = nBu) [73],... 

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... 

Scheme 7.19. Mannich-type multicomponent synthesis of propargylamines.

Tab. 7.6. Multicomponent synthesis of propargylamines using an ionic liquid and r... 

Cu(l)-modified zeolites, especially Cu(I)-USY, proved to be very efficient catalyst in multicomponent reaction. Such catalysts allowed for an efficient, solvent-free synthesis of propargylamines from aldehydes, amines and terminal alkynes with high yields. 

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. 

SCHEME 341 Synthesis of propargylamines by Cu-catalyzed KA -coupling reaction. 

SCHEME 3.42 ACcoupling synthesis of propargylamines using a supported silver-based eatalyst. 

SCHEME 3.50 Asymmetric synthesis of propargylamines by Cu-catalyzed A -couplings. 

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). 

S. B. Park, H. Alper, Chem. Commun. 2005, 1315-1317. An efficient synthesis of propargylamines via C-H activation catalyzed by copperfi) in ionic hquids. 

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. 

K. Layek, R. Chakravarti, M. Lakshmi Kantam, H. Maheswaran, A. Vinu, Green Chem. 2011,13,2878-2887. Nanocrystalline magnesium oxide stabilized gold nanoparticles an advanced nanotechnology based recyclable heterogeneous catalyst platform for the one-pot synthesis of propargylamines. 

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

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. 

D. Aguilar, M. Contel, E. P. Urriolabeitia, Chem.-Eur. J. 2010, 16, 9287-9296. Mechanistic insights into the one-pot synthesis of propargylamines from terminal alkynes and amines in chlorinated solvents catalyzed by gold compounds and nanoparticles. 

Y. He, M.-F. Lv, C. Cai, Dalton Trans. 2012,41,12428-12433. A simple procedure for polymer-supported N-heterocychc carbene silver complex via click chemistry an efficient and recyclable catalyst for the one-pot synthesis of propargylamines. 

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... 

A Mannich-type reaction of j0-keto ester with C-alkynyl imines generated in situ delivers asymmetric synthesis of propargylamines with two adjacent stereocentres organocatalytically. " ... 

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. 

SCHEME 3.18 Silver-catalyzed synthesis of propargylamines through a multicomponent... 

Scheme 4.21 Synthesis of propargylamines from terminal allgmes and N,N-dimethylaiylamines.

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