Stereoselective Construction of ß-chiral Homoallyl Functionalities by Substrate- and Reagent-Controlled Iterative 1,2-Metallate Rearrangements.

Homoallylic alcohols possessing chiral ß-centers are considered highly valuable in the synthesis of polyketide-based natural products. Therefore, there is a significant demand for new methods that allow for their stereoselective access. In pursuit of this objective, we have successfully combined our substrate-controlled protocol of Hoppe-Matteson-Aggarwal chemistry with iterative 1,2-metallate rearrangements. Notably, this approach has proven effective in introducing not only primary alcohols but also other functional groups such as alkynes and protected amines.

1,2-Metallate Rearrangement as a Toolbox for the Synthesis of Allylic Alcohols.

The development of new methods and protocols for the synthesis of biologically active substances remains one of the most important pillars in organic chemistry, and one of these privileged structural motifs are allylic alcohols. The method of choice to date for the synthesis of these is the Nozaki-Hiyama-Takai-Kishi reaction. We describe here a valuable alternative to the synthesis of allylic alcohols via 1,2-metallate rearrangement. In this work, various vinyl boronic esters with different functional groups have been applied in the Hoppe-Matteson-Aggarwal reaction. In addition, two monoterpenoids were constructed via this convergent synthetic strategy.