Hong Allen Y, Vanderwal Christopher D
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697-2025, USA.
Tetrahedron. 2017 Jul 20;73(29):4160-4171. doi: 10.1016/j.tet.2016.11.004. Epub 2016 Nov 3.
Driven by a new biogenetic hypothesis, the first total synthesis of alsmaphorazine B and several related indole alkaloids has been achieved. Numerous early approaches proved unsuccessful owing to unproductive side reactivity; nevertheless, they provided important clues that guided the evolution of our strategy. Critical to our success was a major improvement in our Zincke aldehyde cycloaddition strategy, which permitted the efficient gram-scale synthesis of akuammicine. The sequential chemoselective oxidations of akuammicine leading up to the key oxidative rearrangement also yielded several biogenetically related indole alkaloids to alsmaphorazine B.
在一种新的生物合成假说的推动下,首次实现了阿尔斯马福拉嗪B和几种相关吲哚生物碱的全合成。由于存在无成效的副反应,许多早期方法都未成功;然而,它们提供了重要线索,指导了我们策略的演变。我们成功的关键在于对我们的锌克醛环加成策略进行了重大改进,这使得高效克级合成阿库铵碱成为可能。通向关键氧化重排的阿库铵碱的连续化学选择性氧化还产生了几种与阿尔斯马福拉嗪B具有生物合成关系的吲哚生物碱。