The first total synthesis of (-)-maoecrystal Z is described. The key steps of the synthesis include a diastereoselective Ti(III)-mediated reductive epoxide coupling reaction and a diastereoselective Sm(II)-mediated reductive cascade cyclization reaction. These transformations enabled the preparation of (-)-maoecrystal Z in only 12 steps from (-)-γ-cyclogeraniol.

A practical stereoselective synthesis of cytotoxic anhydrophytosphingosine pachastrissamine (jaspine B) was achieved in 48% overall yield from D-(-)-tartaric acid. Key features of the sequence include the diastereoselective formation of a tetrol with three contiguous chiral centers, which was further elaborated to pachastrissamine. The synthetic route is operationally simple, diastereoselective...

[reaction: see text] Treatment of hydroxy-substituted silyl epoxides with Grignard reagents induces a 1,2-carbon shift to reveal alpha-silyl aldehydes, which are trapped by highly diastereoselective addition reactions of the Grignard reagent. The starting epoxides are readily accessible from propargylic alcohols by regio- and diastereoselective hydrosilylation and epoxidation reactions. In addi...

Total synthesis of (±)-antroquinonol D, which is isolated from very expensive and rarely found Antrodia camphorata and which has potential anticancer properties, was achieved from 4-methoxyphenol. In addition, a Michael addition to dimethoxy cyclohexadienones was studied. The main step involved chelation and substrate-controlled diastereoselective reduction of cyclohexenone and lactonization. L...

An efficient diastereoselective approach for the synthesis of functionalized 3,4-dihydro-2H-pyran-4-carboxamides with variable frame was developed based on the reaction of available 4-oxoalkane-1,1,2,2-tetracarbonitriles (adducts of TCNE and ketones) with aldehydes in an acidic media. An unusual process of quasi hydrolysis of the cyano group was observed in the course of the described regio- an...

A concise and efficient approach for the diastereoselective total synthesis of salvileucalin C, as well as their biosynthetically related diterpenoids salvileucalin D, salvipuberulin, isosalvipuberulin, and dugesin B, has been reported for the first time. The key features of the strategy are based on a Beckwith-Dowd ring expansion, a tandem diastereoselective Stille coupling/debromination/desil...

The asymmetric synthesis of substituted pyrrolidines has been accomplished using a novel organocatalytic cyclization reaction promoted by a Cinchona alkaloid based primary amine. The reaction proceeds smoothly yielding pyrrolidine-2,2-dicarboxylates after in situ diastereoselective reduction with high levels of enantioselection. Furthermore, these adducts could be easily transformed into N-prot...

A diastereoselective and modular approach to the synthesis of the 3-hydroxymethyl-2,3,5,6,7,7a-hexahydro-1H-pyrrolizine-1,2,7-triol structure, characteristic of several natural pyrrolizidine natural products, has been developed. This approach culminated in the synthesis of (-)-7-epiaustraline and (+)-1,7-diepiaustraline. The oxazolidinone group has been found to be a useful protecting group in ...

The first non-chiral pool total synthesis of (+)-hyacinthacine A(1) is described. This synthesis is based on an effective [2 + 2] cycloaddition of dichloroketene to a Stericol-based enol ether, a diastereoselective dihydroxylation, and an efficient Tamao-Fleming oxidation.