Total Synthesis of Nesteretal A.

The enantioselective total synthesis of nesteretal A was achieved in 15 steps via biomimetic cascade hemiacetalizations at the final key step. Other key features of the total synthesis include Sharpless asymmetric dihydroxylation, diastereoselective 1,2-addition, Pd-catalyzed ene-type cyclization, and stereoselective epoxidation to construct a complex structure containing multiple quaternary carbons.