The Total Synthesis of Chondrochloren A

The first total synthesis of chondrochloren A is accomplished using a 1,2‐metallate rearrangement addition as an alternative for the Nozaki‐Hiyama‐Kishi reaction. This transformation also avoids the inherent challenges of this polyketide segment and provides a new, unprecedented strategy to assemble polyketidal frameworks. The formation of the Z‐enamide is accomplished using a Z‐selective cross coupling of the corresponding amide to a Z‐vinyl bromide. A powerful alternative to the Nozaki‐Hiyama‐Kishi reaction serves as the key transformation in the total synthesis of chondrochloren A. Using a novel combination of the Hoppe anion in Matteson rearrangements serves to overcome the inherent synthetic challenges of the polyketide portion of chondrochloren A and paves the way to its total synthesis. Remarkably, this transformation can be performed stereoselectively in the absence of sparteine.