(Z,Z)-Selanediylbis(2-propenamides): Novel Class of Organoselenium Compounds with High Glutathione Peroxidase-Like Activity. Regio- and Stereoselective Reaction of Sodium Selenide with 3-Trimethylsilyl-2-propynamides

The efficient regio- and stereoselective synthesis of (Z,Z)-3,3′-selanediylbis(2-propenamides) in 76–93% yields was developed based on the reaction of sodium selenide with 3-trimethylsilyl-2-propynamides. (Z,Z)-3,3′-Selanediylbis(2-propenamides) are a novel class of organoselenium compounds. To date, not a single representative of 3,3′-selanediylbis(2-propenamides) has been described in the literature. Studying glutathione peroxidase-like properties by a model reaction showed that the activity of the obtained products significantly varies depending on the organic moieties in the amide group. Divinyl selenide, which contains two lipophilic cyclohexyl substituents in the amide group, exhibits very high glutathione peroxidase-like activity and this compound is considerably superior to other products in this respect.

(2Sp,4R,8Sp)-4-Methyl-1-phenyl-diferroceno-5-Z-ethylene-1-phosphinoxide

We present a synthesis of the title compound, a homochiral diferroceno cycle intended for use in asymmetric catalysis. We present a hydrovinylation protocol, which allows the production of the title compound in two steps from a known diferrocenyl precursor. We obtained one of two possible diastereomers selectively and propose a plausible regio- and stereoselective reaction mechanism.

Synthesis and Application of 1,2-Aminoalcohols with Neoisopulegol-Based Octahydrobenzofuran Core

A library of 1,2-aminoalcohol derivatives with a neoisopulegol-based octahydrobenzofuran core was developed and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The allylic chlorination of (+)-neoisopulegol, derived from natural (–)-isopulegol followed by cyclization, gave the key methyleneoctahydrobenzofuran intermediate. The stereoselective epoxidation of the key intermediate and subsequent oxirane ring opening with primary amines afforded the required 1,2-aminoalcohols. The ring closure of the secondary amine analogues with formaldehyde provided spiro-oxazolidine ring systems. The dihydroxylation of the methylenetetrahydrofuran moiety with OsO4/NMO (4-methylmorpholine N-oxide) resulted in the formation of a neoisopulegol-based diol in a highly stereoselective reaction. The antimicrobial activity of both the aminoalcohol derivatives and the diol was also explored.

Enantiomerically Enriched Tetrahydropyridine Allyl Chlorides

Enantiomerically enriched allyl halides are rare due to their configurational lability. Here we report stable piperidine-based allyl chloride enantiomers. These allyl chlorides can be produced via resolution, and undergo highly enantiospecific catalyst-free substitution reactions with C, N, O and S-based nucleophiles. Deuterium-labelled chloro-tetrahydropyridine, selectively prepared using the H/D primary kinetic isotope effect, and DFT calculations were used to investigate the mechanisms of the reactions. The allyl chlorides may also serve as valuable mechanistic tools for probing stereoselective reaction pathways.

Enantiomerically Enriched Tetrahydropyridine Allyl Chlorides

Enantiomerically enriched allyl halides are rare due to their configurational lability. Here we report stable piperidine-based allyl chloride enantiomers. These allyl chlorides can be produced via resolution, and undergo highly enantiospecific catalyst-free substitution reactions with C, N, O and S-based nucleophiles. Deuterium-labelled chloro-tetrahydropyridine, selectively prepared using the H/D primary kinetic isotope effect, and DFT calculations were used to investigate the mechanisms of the reactions. The allyl chlorides may also serve as valuable mechanistic tools for probing stereoselective reaction pathways.

A New Synthetic Route to Polyhydrogenated Pyrrolo[3,4-b]pyrroles by the Domino Reaction of 3-Bromopyrrole-2,5-diones with Aminocrotonic Acid Esters

A new synthetic approach to polyfunctional hexahydropyrrolo[3,4-b]pyrroles was developed based on cyclization of N-arylbromomaleimides with aminocrotonic acid esters. A highly chemo- and stereoselective reaction is a Hantzsch-type domino process, involving the steps of initial nucleophilic C-addition or substitution and subsequent intramolecular nucleophilic addition without recyclyzation of imide cycle.