Diastereo- and Enantioselective Synthesis of Polyfunctional Ketones with Adjacent Quaternary and Tertiary Centers by Asymmetric Carroll Rearrangement

Na . The first asymmetric Carroll rearrangement via dienolate intermediates derived from β‐ketoesters 1 provides access to highly functionalized ketones 2 of high diastereo‐and enantiomeric purity. The chiral auxiliary in this [3,3]sigmatropic rearrangement is (S)‐1‐amino‐2‐methoxymethylpyrrolidine (SAMP). The products 2 with adjacent quaternary and tertiary stereogenic centers show promise as versatile building blocks for natural product and drug synthesis.