Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208, United States.
Department of Chemistry and Biochemistry, Florida Atlantic University, Boca Raton, Florida 33431, United States.
J Org Chem. 2020 May 1;85(9):6201-6205. doi: 10.1021/acs.joc.0c00555. Epub 2020 Apr 23.
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.
Briarellins 是 C2-C11 环化的柏木烷类的一个子集，据推测含有 C3-C14 醚或内酯桥，类似于asperstinins。然而，对 briarellin J 的提议结构的全合成揭示了一个错误的归属。我们借助最近开发的混合 DFT/参数方法 DU8+，从计算的角度重新研究了 briarellins，并将 briarellin C14-C3 ε-内酯的结构修订为新的结构类型，其中包含 C14-C11 或 C14-C12 内酯桥。确认了 briarellin 和 asbestinin 醚的原始结构。
