Biomimetic total synthesis of homodimericin A

Long, Xinyu; Huang, Yunhong; Yang, Long; Deng, Jun

doi:10.1039/c7qo01161j

Cited by 14 publications

(11 citation statements)

References 27 publications

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“…synthetic sample of homodimericin A, which offered an unequivocal evidence for its identity. Beside our work, three other biomimetic syntheses of homodimericin A were also completed by the Wang, 15 Yang, 16 and Deng 17 groups in a short period of time, among which the one completed by Wang and co-workers is particularly notable. In their work, the authors achieved the homodimerization of the para-quinone 14a, the intramolecular Diels-Alder reaction and the carbonyl-ene cyclization in one pot under mild conditions (PBS buffer, air, room temperature), albeit in a relatively low yield.…”

Section: Template For Synlett Thiemementioning

confidence: 96%

Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Tang

Liu

2022

Synlett

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Nature has been recognized for her super capability of constructing complex molecules with remarkable efficiency and elegancy. Among nature’s versatile synthetic toolkits, Diels-Alder reaction is particularly attractive since it allows for rapid generation of molecular complexity from simple precursors. For natural products biosynthetically formed through Diels-Alder reactions, the most straightforward way to access them should build on biomimetic Diels-Alder reactions. However, the implementation of biomimetic Diels-Alder reactions in a laboratory setting may encounter considerable challenges, particularly for those suffering from complicated reactivity and selectivity issues. Indeed, the translation of a biosynthetic hypothesis into a real biomimetic synthesis entails the orchestrated combination of nature’s inspiration and chemist’s rational design. In this account, we will briefly summarize our recent progress on the application of biomimetic Diels-Alder reactions in natural product synthesis. As shown in the discussed stories, rational manipulation of the structures of biosynthetic precursors plays a crucial role for the successful implementation of biomimetic Diels-Alder reactions. 1 Introduction 2 Biomimetic Synthesis of Rossinone B 3 Biomimetic Synthesis of Homodimericin A 4 Biomimetic Synthesis of Polycyclic and Dimeric Xanthanolides 5 Biomimetic Synthesis of Periconiasins and Pericoannosins 6 Biomimetic Synthesis of Merocyctochalasans 7 Conclusion and outlook

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Section: Template For Synlett Thiemementioning

confidence: 96%

Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Tang

Liu

2022

Synlett

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“…Homodimericin A ( 180 ), a fungal metabolite with homodimerized polyketide having 6,5,6,5,6,5‐fused ring moiety with three adjacent quaternary centres was isolated by Clardy and co‐workers from the soil fungus Trihoderma harzianum . [ 65 ] Deng and co‐workers [ 66a ] reported the biomimetic synthesis of structurally complex homodimericin A ( 180 ) in a protection free manner (Scheme 20). Benzyl alcohol 175 (prepared from 2,6‐dimethoxytoluene in 4 steps) [ 67 ] was transformed to the corresponding bromide and further treatment with trimethylsilylated cyanohydrin 176 delivered ketone 177 .…”

Section: Cascade Biomimetic and Enzymatic Approaches In Pgf Totalmentioning

confidence: 99%

“…The synthesis displays a fine art in achieving the PGF total synthesis in a biomimetic cascade and required 7 steps to complete with 4 % overall yield from 175 . An earlier biomimetic cascade synthesis involving protecting groups by Wang [ 66b ] in 2017 also required 7 steps and had overall yield of 4 %. At the same time (2017) other syntheses by Lan [ 66c ] involved 7 steps (3.6 % overall yield) and then by Tang [ 66d ] in 11 steps and 3 % overall yield.…”

Section: Cascade Biomimetic and Enzymatic Approaches In Pgf Totalmentioning

confidence: 99%

Evolution of Strategies in Protecting‐Group‐Free Synthesis of Natural Products: A Recent Update

2020

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The synthesis of complex natural products must be realized with high economy and efficiency, contributing largely to sustainable development in synthetic organic chemistry. The new strategies should adopt protecting‐group‐free approaches enabling step‐economy and thereby enhancing efficiency. Various approaches based on chiral pool, auxiliary‐based methods, cascade, biomimetic, enzymatic and photocatalytic used in total synthesis of natural products and following the PGF‐criteria over the last two years (2018–2019) have been reviewed here. These should guide sustainable synthesis of natural products in the future.

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“…Two other research groups in China published their syntheses of homodimericin A together with our work. 24 The groups of Yang and Lan provided mechanistic insights of the dimerization and Diels-Alder process with the help of computational chemistry. 25 Tang's group obtained crystal structures of some intermediates, including dimethyl-homodimericin A (63) (Scheme 11).…”

Section: Ma Z Wangmentioning

confidence: 99%

Biomimetic Approaches: Synthesis of (±)-Homodimericin A

Wang

2018

Synlett

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A brief history of biomimetic total synthesis is reviewed. The molecules covered in this SynPact account include tropinone (Robinson, 1917), usnic acid (Barton, 1956), progesterone (Johnson, 1971), endiandric acids (Nicolaou, 1982), methyl homosecodaphniphyllate (Heathcock, 1988), glabrescol (Corey, 2000), FR182877 (Sorensen, 2002 and Evans, 2002), and intricarene (Pattenden, 2006 and Trauner, 2006). Key biomimetic transformations of the syntheses are highlighted. Our recent biomimetic synthesis of homodimericin A is also discussed. Our study validates the key steps of the biosynthesis proposed by Clardy et al.

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Biomimetic total synthesis of homodimericin A

Abstract: A practical total synthesis of homodimericin A has been achieved in 7 steps.

Cited by 14 publications

References 27 publications

Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Evolution of Strategies in Protecting‐Group‐Free Synthesis of Natural Products: A Recent Update

Biomimetic Approaches: Synthesis of (±)-Homodimericin A

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