Protocol for (E)-selective semihydrogenation of alkynes using iridium-based catalyst.

In this protocol, we describe highly (E)-selective alkyne semihydrogenation employing commercially available iridium complex and a bidentate phosphine ligand. We provide steps for (E)-stilbene synthesis, remaining formic acid neutralization, and determination of the (Z)/(E) ratio using gas chromatography analysis. We then detail (E)-stilbene purification using a short pad of silica and NMR analysis. The protocol is compatible with a wide range of functionalities and different types of alkynes. For complete details on the use and execution of this protocol, please refer to Kusy et al. (2022).1.

Total synthesis of pipecolic acid and 1-C-alkyl 1,5-iminopentitol derivatives by way of stereoselective aldol reactions from (S)-isoserinal.

A short synthesis of iminosugars and pipecolic acid derivatives has been realized through aldol addition of a pyruvate, a range of ketones and (S)-isoserinal, followed by catalytic reductive intramolecular amination. The stereoselective aldol reaction was achieved successfully by using tertiary amines or di-zinc aldol catalysts, thus constituting two parallel routes to optically pure products with good yields and high diastereoselectivities. These carbohydrate analogues may be the inhibitors of potent glycosidases and glycosyltransferases.

E- and Z-Selective Transfer Semihydrogenation of Alkynes Catalyzed by Standard Ruthenium Olefin Metathesis Catalysts.

Selective transfer semihydrogenation of alkynes to yield alkenes was achieved with commercial first and second generation Hoveyda-Grubbs catalysts and formic acid as a hydrogen donor. This catalytic system is distinguished by its selectivity and compatibility with many functional groups (halogens, cyano, nitro, sulfide, alkenes). The metathetic activity of the ruthenium catalysts may be utilized in tandem sequences of olefin metathesis plus alkyne reduction.