A critical overview of the quickly emerging field of propargylic substitutions is given. This Microreview focuses on experimental results that deal with catalyzed substitutions of propargylic alcohols and their derivatives.

Chiral β-amino carbonyl compounds bearing an α-alkylidene group were easily synthesized under mild and simple conditions from α,β-unsaturated aldehydes and α-amido sulfones in good yields and diastereoselectivities and excellent enantioselectivities.

We have developed an efficient and simple procedure for the cross-coupling of alk-2-enesulfonyl chlorides with Grignard reagents by using 5 mol-% of inexpensive and air stable Fe(acac)₃ as the catalyst in THFat room temperature. Iron-catalyzed reaction of Grignard reagents with functionalized alk-2-enesulfonyl chlorides provided the corresponding cross-coupling products in good yields.

The metal-mediated oxidative coupling of caffeic acid esters has been employed in the biomimetic synthesis of dimeric lignans and neolignans. The manganese-mediated reactions afforded the unusual benzo[kl]xanthene lignans 6 and 15. This route was employed to obtain rufescidride (9) and mongolicumin A (10). A mechanistic study was also carried out.

The synthesis and properties of highly water-soluble meta- and para-carbaborane-containing bis(galactosyl phosphonates) are presented.

(R,R)-DUPHOS-iPr was tested in the asymmetric allylic alkylation reaction using rac-1,3-diphenylpropenyl acetate and a variety of Pd pre-catalysts. Excellent ee values could be obtained. There was a switch in the absolute configuration of the malonate product. DFT calculations were conducted on the active Pd-allyl complexes to identify the most electrophilic site for malonate attack.

A series of isomeric “extended” biphenols based on the terphenyl backbone was synthesized by Suzuki cross-coupling. The ortho isomer (3) and its methylated precursor exist in the form of syn and anti atropisomers at low temperature, which were analyzed by DFT calculations and ¹H NMR spectroscopic studies.

The efficiency of various promoters in intramolecular C–C coupling reactions for the successful direct synthesis of fullerenes under flash pyrolysis conditions has been investigated with benzo[c]phenanthrene as a model system. Fluorine was found to be a promising candidate for efficient intramolecular condensation and seems to provide all the properties required for an “ideal promoter”.

Reactions between malononitrile and cyclopentadiene-protected fused 2-thioxo-1,3-dithiole-p-benzoquinones under different experimental conditions proceed either through the expected Knoevenagel condensation to afford the corresponding TCNQ analogues or through Michael additions with subsequent ring opening of the 1,3-dithiole moiety, leading to ketene imines.

This is a contribution in which a well-known reaction, that is, the coupling between sulfenic acids and thiols, can be regarded as a general methodology for thesynthesis of disulfides, where the S–S bridge links different residues with base-, acid- and temperature-sensitive functional groups. Compound 14 is an example.

Fluorescent chemosensors 6–9, bis-triazoles with a variable length polyoxyethylene chain, have been obtained by click chemistry. Of the 15 metal perchlorate salts screened, compounds 6–9 in MeOH showed selective fluorescence quenching towards only Ag⁺ and Hg²⁺. Under similar conditions, the control compound, a triazolylmethoxymethylpyrene, showed selective fluorescence quenching towards only Hg²⁺.

Pretubulysin, a biosynthetic precursor of the tubulysins, shows potent biological activity in the subnanomolar range towards various tumor cell lines and is therefore an ideal lead structure for the development of tubulysin-based anticancer drugs.

The kinetics of the reactions of primary and secondary amines with benzhydrylium ions and quinone methides have been studied spectrophotometrically in acetonitrileat 20 °C. From the linear free energy relationship log k₂ (20 °C) = s(N + E), the N and s parameters of these amines were determined.

The asymmetric synthesis of a novel tetradentate 1,10-phenanthroline from two starting pyridine subunits with subsequent coupling reactions has been accomplished.The new chiral ligand has been successfully employed in metal-catalyzed epoxide-opening reactions and in enantioselective aminations of β-keto esters.

The ring-opening reactions of aziridine derivatives of 1,6-anhydro-2,3,4-trideoxy-2,3-(tosylepimino)-β-D-hexopyranoses with nucleophiles [azide, halides, haloacids, benzylamine, benzyl alcohol and benzyl mercaptan (BnSH)] were studied, and the regioselectivity and stereoselectivity of the cleavage with respect to the Fürst–Plattner rule were examined.

Pd^II-catalysed cyclization of O-allylic and O-homoallylic trichloroacetimidates provides 4-vinyloxazolines and a 4-vinyldihydrooxazine, respectively. (Z)-Allylic imidates with a secondary δ-acetoxy groupgive (E)-4-vinyloxazolines selectively and with high chirality transfer. The mechanism of the reaction is discussed based on the observed stereoselectivity.