Total synthesis of the triquinane marine sesquiterpene (±)Δ9(12) capnellene using a palladium-catalyzed bis-cyclization step.

Balme, Geneviève; Bouyssi, Didier

doi:10.1016/s0040-4020(01)80763-8

Cited by 72 publications

(24 citation statements)

References 64 publications

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“…In fact, palladium complexes are usually readily available and not very sensitive to oxygen and moisture. This strategy has been successfully applied to alkynes bearing oxygen (Arcadi et al, 1992a;Cavicchioli et al, 1996), nitrogen (Arcadi et al, 1992b; and carbon (Balme and Bouyssi, 1994;Marat et al, 1997) nucleophiles. Cyclization of internal alkynes promoted by organopalladium complexes have proved to be efficient routes to the formation of ring systems (Cacchi et al, 1998;Larock et al, 1998).…”

Section: Resultsmentioning

confidence: 99%

Bicyclic Nucleoside Inhibitors of Varicella-Zoster Virus (VZV): Pd-Catalysed Synthesis of 5-aryl Derivatives and Their Biological Evaluation

Carangio

McGuigan

Andrei

et al. 2001

Antivir Chem Chemother

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We have recently reported the discovery of an entirely new category of potent antiviral agents based on novel deoxynucleoside analogues with unusual fluorescent bicyclic furano base moieties. In order to probe structure activity relationships we prepared a series of 5-aryl derivatives of the lead structures. We herein report the synthesis, characterization, and antiviral evaluation of these novel compounds. 5-Aryl derivatives of the parent nucleosides were synthesized from the corresponding alkynyl deoxyuridines using a simple, versatile and efficient one-step conversion, based on a palladium-catalysed cyclization. As previously noted for the lead compounds, a long alkyl side-chain on the base moiety is essential for antiviral activity. Even with the optimal (C8-C10) side-chain, most of the present compounds are markedly less active than their parent structures. However, some of the synthesized compounds still retained antiviral activity at non-cytotoxic concentrations, being only two- to fivefold less active than the current clinical agent acyclovir. Possible reasons for this structure activity relationship are discussed.

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Section: Resultsmentioning

confidence: 99%

Bicyclic Nucleoside Inhibitors of Varicella-Zoster Virus (VZV): Pd-Catalysed Synthesis of 5-aryl Derivatives and Their Biological Evaluation

Carangio

McGuigan

Andrei

et al. 2001

Antivir Chem Chemother

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“…The conversion of disubstitutedm alonates into gem-dimethyl-bearing quaternary centers is well-known, and generally proceeds by reduction of the malonate to the diol followed by tosylation and deoxygenation with ah ydride reducing agent (Scheme 65). [105] Unlike all of the preceding examples, the extra carbonsf rom the esters are advantageous herea nd although this transformation couldt heoretically be achieved by sequential reductive methylations of ab is(sulfone), this processh as never been reported.…”

Section: Other Sp 3 Dianion Equivalentsmentioning

confidence: 89%

Sulfones as Chemical Chameleons: Versatile Synthetic Equivalents of Small‐Molecule Synthons

Trost

Kalnmals

2019

Chemistry A European J

110

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Sulfones are flexible functional groups that can act as nucleophiles, electrophiles, or even radicals. Changing the reaction conditions can completelya lter the reactivity of as ulfonyl group, and as ar esult, molecules bearing multiple sulfones are versatile building blocks. This Review highlights the unique ability of 1,1-and 1,2-bis(sulfones) to masquerade as av ast array of reactive synthons includingm ethane polyanions, vinyl cations,a nd all-carbond ipoles that would be difficultori mpossible to access directly.Scheme1.Selectedsyntheses and reactions of sulfones.Scheme2.Seminaluse of abis(sulfone) as am ethanedianion equivalent.[a] Prof. 11195 MinireviewScheme5.Pd-catalyzed allylic alkylation reactionsw ith bis(sulfones) as methylanion equivalents.Scheme6.Mitsunobumethylationfacilitated by ab is(sulfone) nucleophile.Scheme7.Formal methyl conjugate additiont oa,b-unsaturated aldehydes.Scheme8.Formal methyl conjugate additiont oa na,b-unsaturated ketone.Scheme11. Organocatalytic asymmetric allylic alkylation of Morita-Baylis-Hillmanc arbonates with FBSM.Scheme12. Formal asymmetric fluoromethylationofa ldimines.Scheme13. Formal asymmetric fluoromethylationofa ldehydes.Scheme14. Formal fluoromethylconjugate additionst oenals.Scheme15. Formal fluoromethylconjugate addition to enones.Scheme16. Alkylation of FBSM with alcohols and alkyl halides.Scheme17. Differential reactivity of BDT in difficult alkylation reactions.Scheme18. Annulative Mitsunobu reactionswith bis(sulfone) nucleophiles.Scheme19. Macrocyclizationr eactionsf acilitated by bis(sulfones). Scheme20. Syntheses of insect pheromones facilitated by bis(sulfones).Scheme21. To talsynthesis of (À)-trans-lauthisan.Scheme22. To talsyntheses of constanolactones Aand B.Scheme56. Usingabis(sulfone) to access an ambiphilic carbonyl synthon.Scheme57. Usingabis(sulfone) to access ac arbonyl diradical synthon.Scheme58. Syntheses of (AE)-21-noribogamineand (AE)-ibogamine facilitated by using abis(sulfone) as areplacement for lowmolecular weight olefins.

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“…The reaction showed a remarkable dependence of regioselectivity on the bulkiness of nucleophiles, which enabled the synthesis of either 5/5 or 6/6 bicyclic systems by just altering the sources of the enolates (Scheme ) . The authors also shrewdly applied the all‐intramolecular cyclization/cross‐coupling process to the synthesis of monounsaturated sesquiterpene, (±)‐Δ 9(12) ‐capnellene (Scheme ) …”

Section: Dicarbofunctionalization Of Tethered Olefins Involving Cyclimentioning

confidence: 99%

Transition Metal‐Catalyzed Dicarbofunctionalization of Unactivated Olefins

Dhungana

Basnet

et al. 2018

The Chemical Record

380

116

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Transition metal (TM)-catalyzed difunctionalization of unactivated olefins with two carbon-based entities is a powerful method to construct complex molecular architectures rapidly from simple and readily available feedstock chemicals. While dicarbofunctionalization of unactivated olefins has a long history typically with the use of either carbon monoxide to intercept C(sp )-[M] (alkyl-TM) species or substrates lacking in β-hydrogen (β-Hs), development of this class of reaction still remains seriously limited due to complications of β-H elimination arising from the in situ-generated C(sp )-[M] intermediates. Over the years, different approaches have been harnessed to suppress β-H elimination, which have led to the development of various types of olefin dicarbofunctionalization reactions even in substrates that generate C(sp )-[M] intermediates bearing β-Hs with a wide range of electrophiles and nucleophiles. In this review, these developments will be discussed both through the lens of historical perspectives as well as the strategies scrutinized over the years to address the issue of β-H elimination. However, this review article by no means is designed to be exhaustive in the field, and is merely presented to provide the readers an overview of the key reaction developments.

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Total synthesis of the triquinane marine sesquiterpene (±)Δ9(12) capnellene using a palladium-catalyzed bis-cyclization step.

Cited by 72 publications

References 64 publications

Bicyclic Nucleoside Inhibitors of Varicella-Zoster Virus (VZV): Pd-Catalysed Synthesis of 5-aryl Derivatives and Their Biological Evaluation

Bicyclic Nucleoside Inhibitors of Varicella-Zoster Virus (VZV): Pd-Catalysed Synthesis of 5-aryl Derivatives and Their Biological Evaluation

Sulfones as Chemical Chameleons: Versatile Synthetic Equivalents of Small‐Molecule Synthons

Transition Metal‐Catalyzed Dicarbofunctionalization of Unactivated Olefins

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