Brominative cyclisation of nerolidol and geranyl-linalool

Kato, Tadahiro; Ishii, Koichi; Ichinose, Isao; Nakai, Yoko; Kumagai, Takashi

doi:10.1039/c39800001106

Cited by 22 publications

(24 citation statements)

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“…52 In the reaction methyl farnesate was reacted with NBS in a mixture of water and tetrahydrofuran, to produce small quantities of a brominated bicyclic ester despite the presence of competing nucleophiles. 55 In addition, the first enantiospecific synthesis of the brominated marine natural product (Ϫ)-aplysistatin derived from (R)-(ϩ)-malic acid involved using a bromonium ion induced cyclization reaction [Scheme 7]. 56 An important feature of the biomimetic reactions is the lack of competing nucleophiles, such as water to quench the bromonium ion intermediate.…”

Section: Biosynthesis Of Halogenated Cyclic Terpenesmentioning

confidence: 99%

The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products

2004

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Halogenated natural products are frequently reported metabolites in marine seaweeds. These compounds span a range from halogenated indoles, terpenes, acetogenins, phenols, etc., to volatile halogenated hydrocarbons that are produced on a very large scale. In many cases these halogenated marine metabolites possess biological activities of pharmacological interest. Given the abundance of halogenated marine natural products found in marine organisms and their potentially important biological activities, the biogenesis of these compounds has intrigued marine natural product chemists for decades. Over a quarter of a century ago, a possible role for haloperoxidase enzymes was first suggested in the biogenesis of certain halogenated marine natural products, although this was long before haloperoxidases were discovered in marine organisms. Since that time, FeHeme- and Vanadium-haloperoxidases (V-HPO) have been discovered in many marine organisms. The structure and catalytic activity of vanadium haloperoxidases is reviewed herein, including the importance of V-HPO-catalyzed bromination and cyclization of terpene substrates.

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Section: Biosynthesis Of Halogenated Cyclic Terpenesmentioning

confidence: 99%

The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products

2004

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“…Following their initial report on TBCO as ab rominative cyclization reagent, [107] Kato and co-workers attempted abiomimetic synthesis of a-a nd b-snyderols (276 and 2)v ia the bromonium-induced cyclization of nerolidol (275). [108] The yields of the natural products were low,a nd it is unclear to what extent the cyclizations were diastereoselective with respect to the tertiary alcohol stereogenic center.Much of the mass balance of the reaction consisted of bromoetherification products of the central alkene (not shown), demonstrating that brominative carbocyclizations are generally unable to compete with heterocyclizations.…”

Section: Stereospecific Halonium-induced Polyene Cyclization 241 Dmentioning

confidence: 99%

Stereoselective Halogenation in Natural Product Synthesis

2016

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At last count, nearly 5000 halogenated natural products have been discovered. In approximately half of these compounds, the carbon atom to which the halogen is bound is sp3‐hybridized; therefore, there are an enormous number of natural products for which stereocontrolled halogenation must be a critical component of any synthesis strategy. In this Review, we critically discuss the methods and strategies used for stereoselective introduction of halogen atoms in the context of natural product synthesis. Using the successes of the past, we also attempt to identify gaps in our synthesis technology that would aid the synthesis of halogenated natural products, as well as existing methods that have not yet seen application in complex molecule synthesis. The chemistry described herein demonstrates yet again how natural products continue to provide the inspiration for critical advances in chemical synthesis.

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“…Whereas we previously demonstrated the utility of this solvolytic methodology in the total synthesis of the brominated chamigrene sesquiterpenes, we sought to demonstrate that this methodology could be applied toward the scalable synthesis of a brominated polycyclic natural product (Scheme ). We targeted the bicyclic, brominated ether 34 , which we believed could be accessed in a straightforward fashion from bromolactone ent -23b . Solvolysis of di- tert -butyl malonate bromochloride ent - 23a on 5.7 g scale proceeded smoothly, and a subsequent decarboxylation step on the crude material cleanly afforded bicyclic bromolactone ent - 23b in 75% yield as a single isolated diastereomer, with complete enantiospecificity, over two steps.…”

Section: Substrate Scope and Applicationsmentioning

confidence: 99%

Enantiospecific Solvolytic Functionalization of Bromochlorides

et al. 2017

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Herein we report that under mild solvolytic conditions, enantioenriched bromochlorides can be ionized, stereospecifically cyclized to an array of complex bromocyclic scaffolds, or intermolecularly trapped by exogenous nucleophiles. Mechanistic investigations support an ionic mechanism wherein the bromochloride serves as an enantioenriched bromonium surrogate. Several natural product-relevant motifs are accessed in enantioenriched form for the first time with high levels of stereocontrol, and this technology is applied to the scalable synthesis of a polycyclic brominated natural product. An array of nucleophiles including olefins, alkynes, heterocycles, and epoxides are competent traps in the bromonium-induced cyclizations, leading to the formation of enantioenriched mono-, bi-, and tricyclic products. This strategy is further amenable to intermolecular coupling between cinnamyl bromochlorides and a diverse set of commercially available nucleophiles. Collectively this work demonstrates that enantioenriched bromonium chlorides are confiugurationally stable under solvolytic conditions in the presence of a variety of functional groups.

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Brominative cyclisation of nerolidol and geranyl-linalool

Cited by 22 publications

References 0 publications

The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products

The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products

Stereoselective Halogenation in Natural Product Synthesis

Enantiospecific Solvolytic Functionalization of Bromochlorides

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