6943-49-3

Upstream product

• 75-64-9 tert-butylamine 
• 106-96-7 propargyl bromide 
• 2450-71-7 Propargylamine 
• 1138742-04-7 N-tert-butyl-(2,2-dibromopropyl)amine 

Downstream Products

• 245342-85-2 N-tert-butyl-3-phenyl-N-prop-2-ynylacrylamide 
• 245342-72-7 N-tert-butyl-N-[3-(1-hydroxy-2,3-diisopropoxy-4-oxocyclobut-2-enyl)prop-2-ynyl]-3-phenylacrylamide 
• 67669-81-2 N-tert-Butyl-3,4-dichloro-N-prop-2-ynyl-benzamide 

Relevant academic research and scientific papers

Triggering the Antitumor Activity of Acyclic Enediyne through Maleimide-Assisted Rearrangement and Cycloaromatization

Acyclic enediynes are generally inactive under physiological conditions to be used as antitumor agents like their natural enediyne counterparts. A new mechanism named as maleimide-assisted rearrangement and cycloaromatization (MARACA) is uncovered to trigger the reactivity of acyclic enediynes. Through this mechanism, cascade 1,3-proton transfer processes are accelerated with the maleimide moiety at the ene position to enable the acyclic enediynes to undergo cycloaromatization and generate reactive radicals under physiological conditions. Computational studies suggest that the highest energy barrier for MARACA is 26.0 kcal/mol, much lower than that of Bergman cyclization pathway (39.6 kcal/mol). Experimental results show that maleimide-based enediynes exhibit low onset temperature, fast generation of radical species at 37 °C, and much faster reaction in aqueous solution than in nonpolar solvent, which is beneficial to achieve both high reactivity in physiological environment and high stability for storage and delivery in nonpolar media. The generated radical species are capable of causing high percentage of double-strand (ds) DNA cleavage, leading to significant cytotoxicity toward a panel of cancer cell lines with half inhibition concentration down to submicromolar level. Overall, the discovery of the MARACA mechanism provides a platform for designing novel acyclic enediynes with high potency for antitumor applications.

Cascade Vinyl Radical Ipso-Cyclization Reactions and the Formation of α,β-Unsaturated-β-aryl-γ-lactams from N-Propargyl Benzamides

Various N-(2-bromo-allyl) benzamides were used as the starting materials to study vinyl radical cyclization reactions. The vinyl radicals underwent ipso-cyclization, fragmentation, and cyclization reactions to produce β-aryl-γ-lactams with the carbonyl group remaining intact. To further study this cascade radical reaction, vinyl radicals were generated by the addition of a tributyltin radical to alkyne moieties, followed by radical ipso-cyclization, fragmentation, cyclization, and β-scission reactions with the production of a series of α,β-unsaturated-β-aryl-γ-lactam derivatives. This new type of radical reaction was examined from the substituent effects on both the amino groups and the aryl groups. A bulky tert-butyl substituent on the amino group enhanced the formation of a Z-conformation of the benzamides and facilitated vinyl radical ipso-cyclization reactions. A synthetic method for preparing α,β-unsaturated-β-aryl-γ-lactams from N-propargyl benzamides was developed.

Copper(II)-Catalyzed [4+1] annulation of propargylamines with N,O-acetals: Entry to the synthesis of polysubstituted pyrrole derivatives

Described herein is the CuCl2-catalyzed [4+1] annulation of a variety of propargylamines with N,O-acetals that function as a C1 unit, leading to the production of polysubstituted pyrrole derivatives. Three important features of the N,O-acetal during the [4+1] annulation series via 5-endo-dig cyclization are described: an enolizable substituent adjacent to the central sp3-carbon is required, the central sp3-carbon displays the functions of both an electrophile and a nucleophile, and liberation of the secondary amine smoothly leads to the aromatization. A CuCl2-catalyzed [4+1] annulation of propargylamines with N,O-acetals having an ester, a ketone, and an amide moiety, leading to the facile preparation of polysubstituted pyrrole derivatives is presented. This annulation series was achieved through 5-endo-dig cyclization and subsequent aromatization in one pot.

Synthesis of novel triazole-linked mefloquine derivatives: Biological evaluation against Plasmodium falciparum

Using 2,8-bis(trifluoromethyl)quinoline, the pharmacophore of mefloquine, as scaffold, eleven novel triazole-linked compounds have been synthesised by the application of CuAAC chemistry. The in vitro biological activity of the compounds on the Plasmodium falciparum chloroquine-sensitive strain NF54 was then determined. The compounds all showed IC50s in the lower μM range with (1R,3S,5R)-N-{[1-(2,8-bis(trifluoromethyl)quinoline-4-yl)-1H-1,2,3-triazol-4-yl]methyl}adamantan-2-amine (29) exhibiting the best activity of 1.00 μM.

Highly regioselective synthesis of substituted isoindolinones via ruthenium-catalyzed alkyne cyclotrimerizations

(Cyclooctadiene)(pentamethylcyclopentadiene) ruthenium chloride [Cp*RuCl (cod)] has been used to catalyze the regioselective cyclization of amide-tethered diynes with monosubstituted alkynes to give polysubstituted isoindolinones. Notably, the presence of a trimethylsilyl group on the diyne generally led to complete control over the regioselectivity of the alkyne cyclotrimerization. The cyclization reaction worked well in a sustainable non-chlorinated solvent and was tolerant of moisture. The optimized conditions were effective with a diverse range of alkynes and diynes. The 7-silylisoindolinone products could be halogenated, protodesilylated or ring opened to access a range of usefully functionalized products.

New xanthate-based radical cyclization onto alkynes

To bypass the failure of radical cyclization involving a xanthate transfer on alkynes, a new reductive cyclization strategy has been completed with the use of a stoichiometric amount of dilauroyl peroxide in isopropanol. When the starting xanthates are prepared via a Ugi 4-component reaction with propargylamine, exomethylene lactams are formed in good yields. The Royal Society of Chemistry.

Synthesis and reactivity of alkenyl- and alkynyl-substituted β,β-dihalo-and?β,β,β-trichloroamines

β,β-Dihalo- and β,β,β-trichloroamines, obtained by Lewis acid-promoted Petasis-type reaction of α,α-dichlorinated and α,α,α-trichlorinated imines or reduction of α,α-dihaloaldimines, were subjected to a reactivity study and turned out to be remarkably sta

Gas-phase thermolysis of N-substituted diallyl- and allylpropargylamines

Various diallyl- and allylpropargylamines were pyrolyzed in a stirred-flow reactor at temperatures in the range of 330-500 °C, pressures of 8-16 Torr and residence times of 0·4-2·4 s using toluene as carrier gas. The reaction products were propene, allene and aldimines. The allene to propene ratio changed considerably with the third substituent on the N atom. At conversions in the range 13-55%, the consumption of the amines showed first-order kinetics. The following Arrhenius parameters [A (s-1) and Ea (kj mol-1)] were obtained from the rate coefficients: diallyl-tert-butylamine, log A = 10·32±0·12, Ea = 139±2; diallylneopentylamine, log A = 12·87±0·26, Ea = 168±3; allylpropargyl-tert-butylamine, log A = 10·23±0·18, Ea = 126±2; allylpropargyltosylamine, log A = 13·05±0.36, Ea = 197±5; and allylpropargylphenylamine, log A = 12·10± 0·35, Ea = 162±4. Polar, six-center cyclic transition states are suggested for the elimination of propene and allene, via non-concerted bond breaking-bond forming mechanisms.

"Vinylogs" and "acetylenylogs" of β-adrenergic agents

Vinylogous (Groups III and V) and acetylenologous (Group IV) analogs of the classical β-adrenergic agents - stimulants and blockers - were prepared in order to evaluate the effect of degree of saturation, position of unsaturation and rigidity of the chain