An Approach towards the Synthesis of the Spiroimine Fragment of 13‐Desmethylspirolide C and Gymnodimine A

Guthertz, Alexandre; Lusseau, Jonathan; Desvergnes, Valérie; Massip, Stéphane; Landais, Yannick

doi:10.1002/chem.201804972

Cited by 6 publications

(4 citation statements)

References 73 publications

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“…Hemiacetals also undergo reactions faster with allylmagnesium halides than other reagents (Scheme 110). 212 Attempts to open acetal 267 with either vinylmagnesium chloride or vinyllithium failed to give any product. By contrast, addition of allylmagnesium chloride gave a high yield of addition product 268, although with low diastereoselectivity.…”

Section: Additions To Alkoxy-substitutedmentioning

confidence: 99%

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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This review describes the additions of allylmagnesium reagents to carbonyl compounds and to imines, focusing on the differences in reactivity between allylmagnesium halides and other Grignard reagents. In many cases, allylmagnesium reagents either react with low stereoselectivity when other Grignard reagents react with high selectivity, or allylmagnesium reagents react with the opposite stereoselectivity. This review collects hundreds of examples, discusses the origins of stereoselectivities or the lack of stereoselectivity, and evaluates why selectivity may not occur and when it will likely occur. CONTENTS 4.2.5. Additions to β-Substituted Aldehydes 4.2.6. Additions to Aldehydes with Distant Chelating Groups 4.3. Additions to Cyclic Ketones 4.3.1. Alkoxy-Substituted Cyclic Ketones 4.3.2. Additions to Alkoxy-Substituted Five-Membered-Ring Ketones 4.3.3. Additions to Alkoxy-Substituted Four-Membered-Ring Ketones 4.4. Additions of Allylmagnesium Halides to Cyclic Hemiacetals 5. Diastereoselectivity of Reactions of Allylmagnesium Reagents with Carbonyl Compounds by Felkin−Anh Control 5.1. Felkin−Anh Stereoselectivity 5.2. Additions to α-Chiral Acyclic Ketones 5.3. Additions to Chiral Exocyclic Ketones and Aldehydes 5.4. Additions of Allylmagnesium Halides to Chiral Cyclic Ketones Controlled by Felkin−Anh Selectivity 5.5. Additions of Allylmagnesium Halides to Chiral Acyclic Aldehydes 6. Diastereoselectivity of Reactions with Carbonyl Compounds by Steric Approach Control 6.1. Steric Approach Control and Stereoselectivity

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Section: Additions To Alkoxy-substitutedmentioning

confidence: 99%

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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“…The synthesis of key members of this class of compounds has been the focus of a number of reviews, 17,18 and in recent times, a renewed interest has emerged, with five separate reports of synthetic strategies to access spirocyclic imine systems of the cyclic imine toxins since 2017. [19][20][21][22][23] Since the early 2000s, our group has remained interested in this unique structural motif and have previously published a review on selected synthetic efforts towards the spirocyclic imine unit of the spirolides prior to 2011. 24 Synthetic approaches detailed in that particular review include intermolecular Diels-Alder strategies, 25,26 alkylation-cyclization approaches [27][28][29] and an asymmetric Birch reductive alkylation.…”

Section: Introductionmentioning

confidence: 99%

Synthetic Studies Towards Spirocyclic Imine Marine Toxins Using N-Acyl Iminium Ions as Dienophiles in Diels–Alder Reactions

Freeman

Furkert

et al. 2020

Synlett

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Cyclic imine marine toxins have attracted considerable attention from the synthetic community in the past two decades due to their unique chemical structures and clinically relevant biological activities. This review presents recent efforts of our group in the development of various strategies to efficiently construct the common spirocyclic imine fragments of the cyclic imine toxins. In particular, the use of α,β-unsaturated N-acyl iminium ion dienophiles in Diels–Alder reactions are highlighted, whereby direct access to spirocyclic imine motifs was obtained and important mechanistic details were discovered. Alternative approaches to spirocyclic imine systems involving hydroamination of amino alkynes are also summarized. One such approach led to serendipitous access to N-vinyl amide products, while our most recently reported approach involving an intermolecular Diels–Alder/cross-coupling sequence using novel 2-bromo-1,3-butadienes to access 5,6-spirocyclic imines is also discussed. Additionally, the development of a novel method to construct another challenging motif present in the portimines is also introduced.1 Introduction2 Strategies towards the Spirocyclic Imine Fragment of Cyclic Imine Toxins2.1 Diels–Alder Cycloadditions of α,β-Unsaturated N-Acyl Iminium Dienophiles2.2 Early Studies Using in situ-Generated Iminium Ion Dienophiles2.3 Use of More Stable Iminium Ion Dienophiles for Diels–Alder Reactions2.4 Other Notable Strategies towards Spirocyclic Imines2.5 Recent Efforts towards the 5,6-Spirocyclic Imine Marine Toxin Portimine A2.6 Construction of Another Challenging Motif of Portimine A3 Conclusion and Future Perspectives

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“…As a result, such bicyclic molecules have been utilized in the synthesis of many natural products, such as highly functionalized terpenoids and polyketides. Representative syntheses of natural products and natural-product-related substances, using a bicyclic 𝛾-lactone as a key intermediate, are the total synthesis of biflora-4,10(19),15-trien by Grieco [ 20 ]; the synthesis of the core of pillaromycinone by White [ 21 , 22 ]; the formal synthesis of A-seco mevinic acid by Potier [ 23 ]; the total synthesis of abyssomicin C ( 2 ) by Nicolaou [ 24 , 25 , 26 ]; the synthesis of the core of abyssomicin C ( 2 ) by Maier [ 27 ]; the synthesis of the core of hirsutellone B ( 3 ) by Roush [ 28 ]; the synthesis of truncated superstolide ( 4 ) by Jin [ 29 ]; the total synthesis of taxol ( 5 ) by Nicolaou [ 30 , 31 , 32 , 33 , 34 ]; the synthesis of simplified derivatives of gracilin A ( 6 ) by Romo [ 35 ]; the formal synthesis of triptolide by Sherburn [ 36 ]; a synthetic approach to himbacine by Sherburn [ 37 ]; a synthetic approach to the spirolide upper fragment by Ishihara [ 38 ]; the synthesis of the spirocyclic core of gymnodimime ( 8 ) and desmethylspirolide C ( 9 ) by Landais [ 39 ]; and the total synthesis of farnesin ( 7 ) by Gao [ 40 ].…”

Section: Synthesis Of Bicyclic 𝛾-Lactones Through the Diels–alder Rea...mentioning

confidence: 99%

“…Landais and co-workers also reported an approach to natural products containing spiroimine, desmethylspirolide C, [ 81 ] and gymnodimine [ 83 ] ( Scheme 33 ) [ 39 ]. They prepared the bicyclic 𝛾-lactone 156 in a good yield with high enantioselectivity via Ishihara’s Lewis-acid-template-catalyzed Diels–Alder reaction.…”

Section: Application Of Lewis-acid-templated Diels–alder Reactions To...mentioning

confidence: 99%

Progress in Lewis-Acid-Templated Diels–Alder Reactions

Ishihara

2024

Molecules

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The synthesis of natural products with complicated architectures often requires the use of segments with functional groups that can be structurally transformed with the desired stereogenic centers. Bicyclic 𝛾-lactones have great potential as a suitable segment for natural product synthesis. However, the stereoselective construction of such functionalized bicyclic 𝛾-lactones is not as straightforward as one might expect. The template-mediated Diels–Alder reaction is one of the most powerful and versatile methods for providing bicyclic 𝛾-lactones with high regioselectivity and stereoselectivity. In this reaction, the diene is linked to the dienophile by a temporary tether, allowing the reaction to proceed efficiently, yielding a product that can be used for natural product synthesis. This review describes some important instances of the template-mediated Diels–Alder reaction and its application to the synthesis of biologically active compounds.

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An Approach towards the Synthesis of the Spiroimine Fragment of 13‐Desmethylspirolide C and Gymnodimine A

Cited by 6 publications

References 73 publications

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

Synthetic Studies Towards Spirocyclic Imine Marine Toxins Using N-Acyl Iminium Ions as Dienophiles in Diels–Alder Reactions

Progress in Lewis-Acid-Templated Diels–Alder Reactions

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