Asymmetric Synthesis and Biosynthetic Implications of (+)‐Fusarisetin A

Yin, Jianping; Wang, Cheng; Kong, Lili; Cai, Shujun; Gao, Shuanhu

doi:10.1002/anie.201202455

Cited by 89 publications

(44 citation statements)

References 60 publications

(28 reference statements)

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“…We report herein the details of our synthetic studies of both equisetin ( 1 ) and (+)‐fusarisetin A ( 2 ) based on our proposed biosynthetic hypothesis. We previously demonstrated that oxidation of 1 with Mn(OAc) 3 /O 2 gave peroxyfusarisetin, which could be easily reduced to 2 4c. We now provide evidence that 1 and 2 should derive from the same biogenetic precursor: polyenoylamino acid 3 .…”

Section: Introductionmentioning

confidence: 53%

Biomimetic Synthesis of Equisetin and (+)‐Fusarisetin A

Yin

Kong

Wang

et al. 2013

Chemistry A European J

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(+)-Fusarisetin A belongs to a group of acyl tetramic acid natural products that show potential anticancer activity. Equisetin, a biogenetically related acyl tetramic acid, contains the basic skeleton of (+)-fusarisetin A. We proposed that equisetin and (+)-fusarisetin A share a biosynthetic pathway that starts with naturally occurring (S)-serine and an unsaturated fatty acid. In support of this hypothesis, we have demonstrated that a cyclization sequence involving an intramolecular Diels-Alder reaction followed by a Dieckmann cyclization of polyenoylamino acid yielded equisetin. The aerobic oxidation of equisetin, promoted by either Mn(III)/O2 or a reactive oxygen species (ROS) produced by visible-light chemistry, gave peroxyfusarisetin, which could be easily reduced to (+)-fusarisetin A. We report herein detailed information on the biogenetic synthesis of equisetin and (+)-fusarisetin A.

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Section: Introductionmentioning

confidence: 53%

Biomimetic Synthesis of Equisetin and (+)‐Fusarisetin A

Yin

Kong

Wang

et al. 2013

Chemistry A European J

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“…16 The structures of these compounds were also confirmed by comparison with the known data. 16,17,24,31 …”

Section: Resultsmentioning

confidence: 63%

“…44 It is worth mentioning that, independently of this study, Gao et al recently reported the conversion of (−)-equisetin to (+)-fusarisetin A using Mn(III)/O 2 conditions. 16 …”

Section: Resultsmentioning

confidence: 99%

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Fusarisetin A: scalable total synthesis and related studies

Caro‐Diaz

Lacoske

et al. 2012

Chem. Sci.

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Fusarisetin A (1) is a recently isolated natural product that displays an unprecedented chemical motif and remarkable bioactivities as a potent cancer migration inhibitor. We describe here our studies leading to an efficient and scalable total synthesis of 1. Essential to the strategy was the development of a new route for the formation of a trans-decalin moiety of this compound and the application of an oxidative radical cyclization (ORC) reaction that produces fusarisetin A (1) from equisetin (2) via a bio-inspired process. TEMPO-induced and metal/O2-promoted ORC reactions were evaluated. Biological screening in vitro confirms the reported potency of (+)-1. Importantly, ex vivo studies show that this compound is able to inhibit different types of cell migration. Moreover, the C5 epimer of (+)-1 was also identified as a potent cancer migration inhibitor, while (−)-1 and 2 were found to be significantly less potent. The optimized synthesis is applicable on gram scale and provides a solid platform for analogue synthesis and methodical biological study.

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“…Another nature-inspired synthesis of fusarisetin A has been reported by Gao et al [36,42], which is based on metal-promoted aerobic oxidation of equisetin.…”

Section: Synthesis Of Fusarisetin Amentioning

confidence: 99%