Briarellins, a subset of C2−C11 cyclized cembranoids, were proposed to contain a C3−C14 ether or lactone bridge, similar to asbestinins. However, the total synthesis of the proposed structure of briarellin J revealed a misassignment. We revisited briarellins, computationally, with the help of a recently developed hybrid DFT/parametric method, DU8+, and revised the structures of briarellin C14−C3 ε-lactones to new structural types containing either a C14−C11 or C14−C12 lactone bridge. The original structures of briarellin and asbestinin ethers were confirmed.Note pubs.acs.org/joc
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