Carbocyclization of unsaturated thioesters under palladium catalysis

Thottumkara, Arun P.; Kurokawa, Toshiki; Bois, J. Du

doi:10.1039/c3sc50486g

Cited by 35 publications

(22 citation statements)

References 34 publications

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“…In 2013, the Du Bois group reported an intramolecular cross‐coupling reaction between thioesters and olefins for the preparation of cyclic ketones from unsaturated thioesters (Scheme ) . This method capitalized on the unique reactivity of thioesters with low‐valent palladium catalysts and Cu I salts to form acyl−metal species.…”

Section: Pd‐catalyzed Liebeskind–srogl Cross‐ Coupling Reactions (Fimentioning

confidence: 99%

The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

et al. 2018

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The Pd-catalyzed, Cu I Àcarboxylate-mediated crosscoupling reactiono fo rganosulfur compounds with nucleophilic organometallic reagents is knowna st he Liebeskind-Srogl cross-coupling reaction. Owing to the readily available starting materials and neutral reactionc onditions, it has become an attractive procedure for the formation of carbonÀcarbon bonds, in particularf or cases in whicht radi-tional methods had failed. Since the seminal work of Liebeskind and Srogl in 2000, this reactionh as received intense attentionf rom the synthetic community.I nt his Focus Review,w eh ighlight recent advances in this intriguing cross-coupling reactiona nd its applications in organic synthesis.Scheme1.Liebeskind-Srogl cross-coupling reaction.Scheme2.The original Liebeskind-Sroglc ross-coupling reaction.d ba = dibenzylideneacetone, TFP = tri-2-furanylphosphine [a] Dr.Scheme4.Cross-coupling reaction between a-amino acid thiol esters and organostannanes. Cbz = benzyloxycarbonyl.Scheme5.Cross-coupling reaction between thiol esters and B-alkyl-9-BBN. 9-BBN = 9-borabicyclo[3.3.1]nonane.Scheme6.One-pothydroboration/intramolecular-cross-couplingr eaction between thiol esters and B-alkyl-9-BBN. DIPEA = N,N-diisopropylethylamine.Scheme7.Cross-coupling reaction between thiol esters andorganoindium reagents.Scheme8.Cross-coupling reaction between thiol esters andorganosilicon reagents. TBAF = tetra-n-butylammonium fluoride.Scheme9.Intramolecular cross-coupling reaction between thiol esters and olefins.Scheme38. Cross-coupling reaction between diaryld isulfides and boronicacids/terminal-alkynes.Scheme55. Synthesis of the C 15 ÀC 36 segment of goniodomin A. TBS = tert-butyldimethylsilyl, TBDPS = tert-butyldiphenylsilyl.Scheme56. To talsynthesis of verbenachalcone. MOM = methoxymethyl.Scheme57. Synthesis of enigmol and its stereoisomers. Boc = tert-butyloxycarbonyl.Scheme58. To talsynthesis of (À)-agelastatins A-F.Scheme59. Synthesis of quinone-containing salvinorin Aa nalogues.Scheme60. Synthesis of Soai-type aldehydes.

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Section: Pd‐catalyzed Liebeskind–srogl Cross‐ Coupling Reactions (Fimentioning

confidence: 99%

The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

et al. 2018

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“…Mizoroki-Heck cyclization of benzoic anhydrides,a lbeit without the formation of aq uaternary stereocenter, [9,10] and from Pd-catalyzed carbonylative Mizoroki-Heck reactions of aryl halides and triflates. [11] Herein, we describe the development and scope of aNi-catalyzed Mizoroki-Heck cyclization of amide derivatives.…”

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confidence: 99%

Mizoroki–Heck Cyclizations of Amide Derivatives for the Introduction of Quaternary Centers

et al. 2017

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We report the non-decarbonylative Mizoroki–Heck reactions of amide derivatives. The transformation relies on the use of nickel catalysis and proceeds using sterically hindered tri- and tetrasubstituted olefins to give products containing quaternary centers. The resulting polycyclic or spirocyclic products can be obtained in good yields. Moreover, a diastereoselective variant of this methodology demonstrates its value for accessing adducts bearing vicinal, highly substituted sp3 stereocenters. Our results demonstrate that amide derivatives can be used as building blocks for the assembly of complex scaffolds.

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“…There are several methods which enable the introduction of arylidene group onto the plain tetrahydropyran-4-one ring using a reaction with aromatic aldehydes in the presence of catalytic amount of TMSNMe 2 and MgBr 2 Et 2 O [7] or pyrrolidine [8]. There are also two literature reports which describe preparation of specific 3-methylidenetetrahydropyran-4-ones, and thus 8-methylidene-9oxo-6-oxaspiro [5,6] decane was prepared by carbocyclization of unsaturated thioesters under palladium catalysis [9] and 2-butyl-6,6-dimethyl-3-methylidenetetrahydropyran-4-one was obtained in a three-step reaction sequence starting from 6-ethoxy-2-methyl-5-diphenylphosphorylhex-3-yn-5-en-2-ol [10].…”

Section: Chemistrymentioning

confidence: 99%

Synthesis of 2,2,6-Trisubstituted 5-Methylidene-tetrahydropyran-4-ones with Anticancer Activity

et al. 2020

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In our continuous search for new, relatively simple 2-alkylidene-1-oxoheterocycles as promising anticancer drug candidates, herein we report an efficient synthesis of 2,2,6-trisubstituted 5-methylidenetetrahydropyran-4-ones. These compounds were obtained in a four step reaction sequence, in which starting diethyl 2-oxopropylphosphonate was transformed into 2,2-disubstituted 5-diethoxyphosphoryldihydropyran-4-ones, followed by Michael addition of various Grignard reagents and Horner-Wadsworth-Emmons reaction of the obtained adducts with formaldehyde. Stereochemistry of the intermediate Michael adducts is also discussed. Final 5-methylidenetetrahydropyran-4-ones were tested for their possible antiproliferative effect against three cancer cell lines and 6-isopropyl-2,2-dimethyl-5-methylidenetetrahydropyran-4-one (11c), which showed very high cytotoxic activity against HL-60 human leukemia cells and was three times more active than known anticancer drug carboplatin, was selected for further biological evaluation, in order to disclose its mechanism of action. The obtained results indicated that 11c induced apoptosis in HL-60 cells and caused the arrest of the cell cycle in the G2/M phase, which may suggest its cytotoxic and cytostatic activity.

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Carbocyclization of unsaturated thioesters under palladium catalysis

Cited by 35 publications

References 34 publications

The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

The Liebeskind–Srogl Cross‐Coupling Reaction and its Synthetic Applications

Mizoroki–Heck Cyclizations of Amide Derivatives for the Introduction of Quaternary Centers

Synthesis of 2,2,6-Trisubstituted 5-Methylidene-tetrahydropyran-4-ones with Anticancer Activity

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