Stereocontrolled Synthesis and Structural Revision of Plebeianiol A.

We report the structural revision via synthesis of the abietane diterpenoid plebeianiol A. The synthesis was accomplished via a short and convergent sequence that featured our previously established cobalt-catalyzed hydrogen-atom-transfer-induced radical bicyclization. We further connected plebeianiol A as the likely biogenetic precursor to another, previously reported ether-bridged abietane. Finally, we demonstrated that the key cyclization event is efficient with the A-ring diol protected with two different cyclic acetal protecting groups or in unprotected form.

我们通过对松香烷二萜plebeianiol A的合成报道了其结构修正。该合成是通过一个简短且汇聚的序列完成的，其特点是我们先前建立的钴催化的氢原子转移诱导的自由基双环化反应。我们还将plebeianiol A作为可能的生源前体与另一种先前报道的醚桥连松香烷联系起来。最后，我们证明了关键的环化反应在A环二醇被两种不同的环状缩醛保护基保护或未受保护的形式下都是有效的。