Propargylamines are a versatile class of compounds which find broad application in many fields of chemistry. This review aims to describe the different strategies developed so far for the synthesis of propargylamines and their derivatives as well as to highlight their reactivity and use as building blocks in the synthesis of chemically relevant organic compounds. In the first part of the review, the different synthetic approaches to synthesize propargylamines, such as A3 couplings and C–H functionalization of alkynes, have been described and organized on the basis of the catalysts employed in the syntheses. Both racemic and enantioselective approaches have been reported. In the second part, an overview of the transformations of propargylamines into heterocyclic compounds such as pyrroles, pyridines, thiazoles, and oxazoles, as well as other relevant organic derivatives, is presented.

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Synthesis and Reactivity of Propargylamines in Organic Chemistry

The direct introduction of fluorine and fluorinated building blocks has recently attracted a lot of attention and particularly the direct functionalization of alkenes and alkynes. This review will highlight the major progress recently made in that field, with a focus on photocatalyzed transformations, base-promoted processes, and transition metal-catalyzed functionalization of alkenes and alkynes. Special attention will be paid to explanations of the reaction mechanisms.

Recent Progress in Direct Introduction of Fluorinated Groups on Alkenes and Alkynes by means of C ? H Bond Functionalization

The cyclopentenone unit is a very powerful synthon for the synthesis of a variety of bioactive target molecules. This is due to the broad diversity of chemical modifications available for the enone structural motif. In particular, chiral cyclopentenones are important precursors in the asymmetric synthesis of target chiral molecules. This Review provides an overview of reported methods for enantioselective and asymmetric syntheses of cyclopentenones, including chemical and enzymatic resolution, asymmetric synthesis via Pauson-Khand reaction, Nazarov cyclization and organocatalyzed reactions, asymmetric functionalization of the existing cyclopentenone unit, and functionalization of chiral building blocks.

Synthesis of Chiral Cyclopentenones.

Asymmetric carbon-hydrogen (C-H) activation reactions often rely on desymmetrization of prochiral C-H bonds on the same achiral molecule, using a chiral catalyst. Here, we report a kinetic resolution via palladium-catalyzed enantioselective C-H iodination in which one of the enantiomers of a racemic benzylic amine substrates undergoes faster aryl C-H insertion with the chiral catalysts than the other. The resulting enantioenriched C-H functionalization products would not be accessible through desymmetrization of prochiral C-H bonds. The exceedingly high relative rate ratio (k(fast)/k(slow) up to 244), coupled with the subsequent iodination of the remaining enantiomerically enriched starting material using a chiral ligand with the opposite configuration, enables conversion of both substrate enantiomers into enantiomerically pure iodinated products.

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Room-temperature enantioselective C–H iodination via kinetic resolution

A process for tunable and chemo-, regio-, and stereoselective photocatalytic trifluoromethylation of styrenes was developed. Thermodynamically stable E-trifluoromethylated alkenes were prepared using Togni’s reagent in the presence of Ru(bpy)3Cl2·6H2O under visible light irradiation, whereas less thermodynamically stable Z-trifluoromethylated alkenes were obtained by employing Umemoto’s reagent and photocatalyst Ir(ppy)3.

Chemo-, Regio-, and Stereoselective Trifluoromethylation of Styrenes via Visible Light-Driven Single-Electron Transfer (SET) and Triplet–Triplet Energy Transfer (TTET) Processes

Asymmetric Allylation/Pauson–Khand Reaction: A Simple Entry to Polycyclic Amines. Application to the Synthesis of Aminosteroid Analogues

To reconcile the urgent need to access well defined β-configured 2,6-di-deoxypyranose analogues for chemical biology, with the intrinsic α-selectivity of the native system, the directing role of fluorine at C2 has been explored. Localised partial charge inversion (C-H(δ+)→ C-F(δ-)) elicits a reversal of the substrate-based α-stereoselectivity, irrespective of the protecting group electronics.

Fluorine-directed 1,2-trans glycosylation of rare sugars

The reaction between alkynes (I) and norbornadiene (II) affords the β-substituted Pauson—Khand adducts (III) as single regioisomers and the trifluoromethyl steering group can be easily removed in the presence of DBU and water.

Synthesis and application of β-substituted Pauson-Khand adducts: trifluoromethyl as a removable steering group.

Regioselectivity in intermolecular Pauson-Khand reactions of dissymmetric fluorinated alkynes.

http://diposit.ub.edu/dspace/bitstream/2445/50467/1/632485.pdf

Nuria Aiguabella

Papers

Asymmetric Allylation/Pauson–Khand Reaction: A Simple Entry to Polycyclic Amines. Application to the Synthesis of Aminosteroid Analogues

Fluorine-directed 1,2-trans glycosylation of rare sugars

Synthesis and application of β-substituted Pauson-Khand adducts: trifluoromethyl as a removable steering group.

Regioselectivity in intermolecular Pauson-Khand reactions of dissymmetric fluorinated alkynes.

Pauson-Khand adducts of N-Boc-propargylamine: a new approach to 4,5-disubstituted cyclopentenones.