The first stereoselective total synthesis of (−)-(2S,4R)-3′-methoxy citreochlorol and (−)-(2S,4S)-3′-methoxy citreochlorol is demonstrated. A proline-based imidazolidinone was synthesized and used as chiral auxiliary for asymmetric acetate aldol reaction to generate initial chirality in the targeted molecule. Geminal dichloromethane functionality was introduced by the addition of in situ generated dichloromethyllithium to Weinreb’s amide functional group.

A concise, stereoselective and protecting group free approaches for the total synthesis of (−)‐(2S,4R)‐ and (+)‐(2R,4S)‐3′‐methoxyl citreochlorols and their stereoisomers are demonstrated. All four stereoisomers were synthesized to establish the absolute stereochemistry of the reported structures and the structures were revised accordingly. The approach involves chelation controlled regioselective reduction of a diester, silyl iodide promoted ring‐opening iodo esterification of lactones, highly chemo‐ and regioselective ring‐opening of an epoxy ester, dichloromethylation of a carboxyl group, and syn‐ and anti‐selective reduction of the resulted β‐hydroxy ketone as key steps.

First stereoselective total synthesis of (+)-diaportinol, (À )-peniisocoumarin H and (+)-& (À )-desmethyldiaportinol is demonstrated and their absolute stereochemistry was revised accordingly. A convergent approach has been developed that uses L-malic acid as chiral synthons for the synthesis of 2, and D-malic acid for 1 and 3. O,O-Dimethylorsellinic acid ester was prepared and coupled with Weinreb amide 6 or 6D via lateral lithiation carbonylation and a subsequent base catalyzed cyclization provided the isochromenone moiety and a selective deprotection was achieved using BBr 3 .

A concise and stereoselective synthesis of a key fragment C3-C22 unit of tartrolons D and E is demonstrated. Three crucial fragments are combined to form the twenty-carbon chain, which contains four stereogenic centers in the monomeric unit of both natural products. These crucial fragments 9, 10, and 11 were synthesized in highly enantioselective routes from commercial starting compounds in two, eight, and two steps, respectively, and coupled using palladium catalyzed Sonogashira coupling and directed 1,5-asymmetric aldol reaction as key steps.