TY - JOUR
T1 - Asymmetric syntheses of sceptrin and massadine and evidence for biosynthetic enantiodivergence
AU - Ma, Zhiqiang
AU - Wang, Xiaolei
AU - Wang, Xiao
AU - Rodriguez, Rodrigo A.
AU - Moore, Curtis E.
AU - Gao, Shuanhu
AU - Tan, Xianghui
AU - Ma, Yuyong
AU - Rheingold, Arnold L.
AU - Baran, Phil S.
AU - Chen, Chuo
N1 - Publisher Copyright:
Copyright 2014 by the American Association for the Advancement of Science; all rights reserved.
PY - 2014/10/10
Y1 - 2014/10/10
N2 - Cycloaddition is an essential tool in chemical synthesis. Instead of using light or heat as a driving force, marine sponges promote cycloaddition with a more versatile but poorly understood mechanism in producing pyrrole-imidazole alkaloids sceptrin, massadine, and ageliferin. Through de novo synthesis of sceptrin and massadine, we show that sponges may use single-electron oxidation as a central mechanism to promote three different types of cycloaddition. Additionally, we provide surprising evidence that, in contrast to previous reports, sceptrin, massadine, and ageliferin have mismatched chirality. Therefore, massadine cannot be an oxidative rearrangement product of sceptrin or ageliferin, as is commonly believed. Taken together, our results demonstrate unconventional chemical approaches to achieving cycloaddition reactions in synthesis and uncover enantiodivergence as a new biosynthetic paradigm for natural products.
AB - Cycloaddition is an essential tool in chemical synthesis. Instead of using light or heat as a driving force, marine sponges promote cycloaddition with a more versatile but poorly understood mechanism in producing pyrrole-imidazole alkaloids sceptrin, massadine, and ageliferin. Through de novo synthesis of sceptrin and massadine, we show that sponges may use single-electron oxidation as a central mechanism to promote three different types of cycloaddition. Additionally, we provide surprising evidence that, in contrast to previous reports, sceptrin, massadine, and ageliferin have mismatched chirality. Therefore, massadine cannot be an oxidative rearrangement product of sceptrin or ageliferin, as is commonly believed. Taken together, our results demonstrate unconventional chemical approaches to achieving cycloaddition reactions in synthesis and uncover enantiodivergence as a new biosynthetic paradigm for natural products.
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U2 - 10.1126/science.1255677
DO - 10.1126/science.1255677
M3 - Article
C2 - 25301624
AN - SCOPUS:84907821386
SN - 0036-8075
VL - 346
SP - 219
EP - 224
JO - Science
JF - Science
IS - 6206
ER -