Synthesis of Dimethyl Gloiosiphone A by Way of Palladium-Catalyzed Domino Cyclization

Doi, Takayuki; Iijima, Yusuke; Takasaki, Masaya; Takahashi, Takashi

doi:10.1021/jo062546v

Cited by 19 publications

(9 citation statements)

References 27 publications

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“…After reductive cleavageo ft he sulfonyl groups, further elaboration of the core carbon skeleton in 103 eventually gave rise to dimethyl gloiosiphoneA (104). [41] Bis(sulfones)c an also be used to disconnect complexm olecules in the middle of an alkyl chain. By enabling the latestage coupling of fragments of similar complexity,t his strategy can greatly simplify retrosynthetic analyses and can also be used to achieve more convergent syntheses.…”

Section: Secondary Carbon Synthonsmentioning

confidence: 99%

“…Sequential Pd‐catalyzed allylic alkylations of BPSM 4 with allylic acetate 100 and allylic bromide 101 furnished triene 102 , which was transformed into spirocycle 103 by a Pd‐catalyzed cycloisomerization reaction (Scheme ). After reductive cleavage of the sulfonyl groups, further elaboration of the core carbon skeleton in 103 eventually gave rise to dimethyl gloiosiphone A ( 104 ) …”

Section: Synthetic Equivalents Of Sp3 Synthonsmentioning

confidence: 99%

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

Trost

Kalnmals

2019

Chemistry A European J

109

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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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Section: Secondary Carbon Synthonsmentioning

confidence: 99%

Section: Synthetic Equivalents Of Sp3 Synthonsmentioning

confidence: 99%

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

Trost

Kalnmals

2019

Chemistry A European J

109

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“…A similar approach has been developed using a π-allyl palladium intermediate followed by intramolecular 5-exo-trig cyclocarbopalladation leading to dimethyl gloiosiphone A. 32…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Cyclocarbopalladation as a Key Step in Cascade Reactions: Recent Developments

et al. 2017

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Cascade reactions are step-economical processes for the synthesis of complex molecules as they allow, in one step, the formation of multiple bonds. Over the last two decades cyclocarbopalladation has emerged as a powerful key step when integrated into these sequences and has allowed unprecedented valuable polycyclic scaffolds to be obtained. This review is focused on recent developments in this field including original cascade sequences, novel activation modes (C-H activation for instance) and unprecedented families of substrates. 1 Introduction 2 Formation of Carbocycles 2.1 4-exo Cyclocarbopalladation 2.2 5-exo Cyclocarbopalladation 2.3 5-endo Cyclocarbopalladation 2.4 Cyclocarbopalladation with Formation of Six-Membered Carbocycles 2.5 Cyclocarbopalladation with Formation of Seven-Membered Carbocycles 3 Formation of Heterocycles 3.1 Formation of Nitrogen Heterocycles 3.2 Formation of Oxygen Heterocycles 3.3 Formation of Sulfur Heterocycles 3.4 Formation of Silicon-Containing Heterocycles 4 Conclusion

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“…Unfortunately, although bis(sulfones) are easy to introduce, they are not typically desired in the final products and have limited synthetic utility for future steps, as illustrated by several total syntheses that employ this ubiquitous functional group (Scheme ). Often, bis(sulfones) are simply fully reduced to the corresponding alkanes, as is done in the syntheses of (−)‐lauthisan and dimethyl gloiosiphone A …”

Section: Introductionmentioning

confidence: 99%

Sulfones as Synthetic Linchpins: Transition‐Metal‐Free sp³–sp² and sp²–sp² Cross‐Couplings Between Geminal Bis(sulfones) and Organolithium Compounds

Trost

Kalnmals

2018

Chemistry A European J

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A valuable umpolung strategy that highlights the ambiphilic nature of the bis(phenylsulfonyl)methyl synthon and demonstrates its utility as a synthetic linchpin is reported. Although the bis(phenylsulfonyl)methyl group is typically introduced as an sp -carbon nucleophile, it is demonstrated that it can also function as an effective sp -carbon electrophile in the presence of organolithium nucleophiles. Alkyl- and aryllithiums couple with the central carbon of the bis(phenylsulfonyl)methyl unit to ultimately generate trisubstituted alkenes, comprising formal sp -sp and sp -sp cross-couplings between organolithium reagents and bis(sulfones). This process occurs almost instantaneously at -78 °C in the absence of any transition metals. By developing this curious transformation, it has been demonstrated that bis(phenylsulfonyl)methane is a valuable synthetic linchpin, which can undergo two C-C bond-forming processes as an sp -nucleophile, followed by a third C-C bond-forming reaction as an effective sp -electrophile. This discovery significantly enhances the utility of this ubiquitous, but underutilized, linker group.

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Synthesis of Dimethyl Gloiosiphone A by Way of Palladium-Catalyzed Domino Cyclization

Cited by 19 publications

References 27 publications

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

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

Cyclocarbopalladation as a Key Step in Cascade Reactions: Recent Developments

Sulfones as Synthetic Linchpins: Transition‐Metal‐Free sp³–sp² and sp²–sp² Cross‐Couplings Between Geminal Bis(sulfones) and Organolithium Compounds

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Synthesis of Dimethyl Gloiosiphone A by Way of Palladium-Catalyzed Domino Cyclization

Cited by 19 publications

References 27 publications

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

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

Cyclocarbopalladation as a Key Step in Cascade Reactions: Recent Developments

Sulfones as Synthetic Linchpins: Transition‐Metal‐Free sp3–sp2 and sp2–sp2 Cross‐Couplings Between Geminal Bis(sulfones) and Organolithium Compounds

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Sulfones as Synthetic Linchpins: Transition‐Metal‐Free sp³–sp² and sp²–sp² Cross‐Couplings Between Geminal Bis(sulfones) and Organolithium Compounds