Chiral Pool Meets Chiral Catalysis: Eight-Step Convergent Total Synthesis of Anticancer Natural Lipid Mycalol.

An exemplary blend of chiral pool with chiral catalysis is exhibited in an eight-step (longest) convergent asymmetric total synthesis of mycalol, which is a promising anticancer natural lipid from a marine source. The polyhydroxy lipid is constructed by using four blocks, and two of which are derived from the chiral pool (d-mannitol and d-gluconolactone) and the other two by chiral catalysis (Sharpless epoxidation and Keck allylation). Alkylation and metathesis were used to knit the blocks in an excellent display of a modular convergent eight-step synthesis. The modular excess will enable rapid analogue generation as revealed by the convenient synthesis of 4-epi-mycalol similarly in an eight-step sequence.

TBAI-Catalyzed Regioselective Hydroxyperoxidation of 1-Aryl/Alkyl-1,3-dienes.

An efficient, mild, and economical approach for regioselective synthesis of 4-aryl/alkyl-1-peroxy-but-3-en-2-ols from 1-substituted-1,3-butadienes using hydroperoxides and catalyzed by TBAI has been developed. This method can be executed in a simple operation with no dry conditions required and having tolerance to a wide range of substrates to access corresponding hydroxyperoxidates in good yields. Thus, an excellent regioselective orthogonal dioxygenation in a diene system has been achieved.

Palladium-Catalyzed Regioselective Intermolecular Hydroalkoxylation of 1-Arylbutadienes.

An efficient method for the synthesis of (E)-(3-alkoxybut-1-enyl)benzenes by Pd-catalyzed regioselective intermolecular hydroalkoxylation of 1-arylbutadienes has been developed. This method can be executed in a simple operation with no dry reaction conditions required and having tolerance to a wide range of substrates. Chloromethyl methyl ether (MOMCl) as an additive was found to be essential for the success of the reaction.