https://iopscience.iop.org/article/10.1070/RCR4795/pdf

Organofluorine chemistry: promising growth areas and challenges

7,20-Diisocyanoadociane, a scarce marine metabolite with potent antimalarial activity, was synthesized as a single enantiomer in 13 steps from simple building blocks (17 linear steps). Chemical synthesis enabled identification of isocyanoterpene antiplasmodial activity against liver-stage parasites, which suggested that inhibition of heme detoxification does not exclusively underlie the mechanism of action of this class.

Synthesis of (+)-7,20-Diisocyanoadociane and Liver-Stage Antiplasmodial Activity of the Isocyanoterpene Class

Main methods for the synthesis of C-ethynylpyrroles were systematically surveyed and described. The reaction mechanisms behind these methods are considered. The reactivity of C-ethynylpyrroles is discussed, with a main focus on cycloaddition and intramolecular cyclization reactions involving the ethynyl substituent to form new pyrrole systems. The bibliography includes 131 references.

C-Ethynylpyrroles: synthesis and reactivity

N-Vinyl-2-(trifluoroacetylethynyl)pyrroles and E-2-(1-bromo-2-trifluoroacetylethenyl)pyrroles: Cross-coupling vs. addition during CH-functionalization of pyrroles with bromotrifluoroacetylacetylene in solid Al2O3 medium. H-bonding control

Cross-coupling of 2-(biphenyl-4-yl)pyrroles derived from 1-(biphenyl-4-yl)ethanone oximes and acetylene with 3-bromo-1-phenylprop-2-yn-1-one on aluminum oxide gave 3-[5-(biphe-nyl-4-yl)pyrrol-2-yl]-1-phenylprop-2-yn-1-ones in 35–46% yields.

Synthesis of 3-[5-(biphenyl-4-yl)pyrrol-2-yl]-1-phenylprop-2-yn-1-ones by palladium-free cross-coupling between pyrroles and haloalkynes on aluminum oxide

The reactions of 4-chloro-1,1,1-trifluorobut-3-yn-2-one and 4-bromo-1,1,1-trifluorobut-3-yn-2-one with conjugated dienes afford [4+2] cycloadducts in high yields. The halogen atom in the products is readily replaced by a (het)aryl residue in the cross-coupling with organozinc compounds.

4-Halogeno-1,1,1-trifluorobut-3-yn-2-one [4+2] cycloadducts and their cross-coupling with organozinc compounds

Reaction of 4-chloro-1,1,1-trifluorobut-3-yn-2-one with alkyl vinyl ethers leads to the parallel formation of [2+2] cycloaddition and electrophilic alkynylation products, the ratio of which depends on the nature of vinyl ether. Preparative methods for the separation of compounds formed are suggested.

[2+2] Cycloaddition and electrophilic alkynylation reactions of 4-chloro-1,1,1-trifluorobut-3-yn-2-one and alkyl vinyl ethers

Synthesis of novel β-dialkylamino-α,β-unsaturated trifluoromethylketones containing cyclobutene fragment and their reactions with organolithium and Grignard reagents

Reaction of the title butynone (I) with vinyl ethers results in the parallel formation of [2 + 2] cycloaddition and electrophilic alkynylation products in ratios depending on the nature of the vinyl ether.

[2 + 2] Cycloaddition and Electrophilic Alkynylation Reactions of 4‐Chloro‐1,1,1‐trifluorobut‐3‐yn‐2‐one and Alkyl Vinyl Ethers.

Various novel 2-(dialkylamino)cyclobutenyl trifluoromethyl ketones are prepared by amination reaction of the corresponding halides.

Synthesis of Novel β-Dialkylamino-α,β-unsaturated Trifluoromethylketones Containing Cyclobutene Fragment and Their Reactions with Organolithium and Grignard Reagents.

N. P. Tsvetkov

Papers

4-Halogeno-1,1,1-trifluorobut-3-yn-2-one [4+2] cycloadducts and their cross-coupling with organozinc compounds

[2+2] Cycloaddition and electrophilic alkynylation reactions of 4-chloro-1,1,1-trifluorobut-3-yn-2-one and alkyl vinyl ethers

Synthesis of novel β-dialkylamino-α,β-unsaturated trifluoromethylketones containing cyclobutene fragment and their reactions with organolithium and Grignard reagents

[2 + 2] Cycloaddition and Electrophilic Alkynylation Reactions of 4‐Chloro‐1,1,1‐trifluorobut‐3‐yn‐2‐one and Alkyl Vinyl Ethers.

Synthesis of Novel β-Dialkylamino-α,β-unsaturated Trifluoromethylketones Containing Cyclobutene Fragment and Their Reactions with Organolithium and Grignard Reagents.