Enantioselective Synthesis of Functionalised Decalones by Robinson Annulation of Substituted Cyclohexanones, Derived from R-(−)-Carvone

Jansen, B. J. M.; Hendrikx, Cindy C. J.; Masalov, N. V.; Stork, G. A.; Meulemans, Tommi M.; Macaev, Fliur; Groot, Aede de

doi:10.1016/s0040-4020(00)00110-1

Cited by 29 publications

(13 citation statements)

References 17 publications

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“…This apparently lower stability of the vinyl‐substituted compounds might be due to their increased steric congestion. Even treatment of 6 with pyrrolidinium acetate (that is, under typical Knoevenagel conditions, which worked well in the spirocyclization of other sterically congested systems),13c,d,g only resulted in deformylation to the cyclopentanone 18 .…”

Section: Resultsmentioning

confidence: 99%

Spirodionic Acid, a Novel Metabolite from Streptomyces sp., Part 2: Total Synthesis through a Twofold Michael Addition as a Selective Spiroannelation Strategy

Siewert¹,

Textor²,

Grond³

et al. 2007

Chemistry A European J

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To elucidate the structure of the new natural product spirodionic acid, which has three stereogenic centers of hitherto unknown configuration, two 4-ethenylspiro[4.5]dec-6-en-1,8-diones with opposite relative configuration at C4 and C5 were prepared. The first access involved the synthesis of 3-ethenyl-2-formylcyclopentanone (8) using a three-component coupling process. A sequence of Michael addition to penten-3-one (7) and intramolecular aldol condensation then led to the highly selective formation of the 4S*,5S*-configured spirocycle 5. In contrast, a selective spiroannelation of a cyclohexenone ring was accomplished by a novel type of twofold Michael addition to the dialkenyl ketone 11 with subsequent dehydrogenation to furnish the 4S*,5R*-configured spirocycle 25. Diastereoselective methylation and oxidative degradation then completed a highly efficient synthesis of the natural product as prerequisite for the assignment of its absolute configuration.

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Section: Resultsmentioning

confidence: 99%

Spirodionic Acid, a Novel Metabolite from Streptomyces sp., Part 2: Total Synthesis through a Twofold Michael Addition as a Selective Spiroannelation Strategy

Siewert¹,

Textor²,

Grond³

et al. 2007

Chemistry A European J

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“…However, the formation of a mixture (1:10) of diastereomeric diketones prepared by Wacker oxidation of the double bond in oxodiene 131 was observed [55,56]. Ketone 145 was used as a substrate in the synthesis of optically pure natural compounds [58][59][60][61][62][63], for example, to prepare clerodanes, namely dihydroclerodane (147) and lupulin C (148), diterpenoids with broad spectra of biological activity (antiviral, antiseptic, antitumor, antiulcer, etc.) The second ring was constructed by intramolecular Robinson annelation.…”

Section: Use Of 12-adducts Of Cyclic αβ-Enone Monoterpenoids and Ormentioning

confidence: 99%

“…The second ring was constructed by intramolecular Robinson annelation. The synthetic potential of (R)-1 was expanded based on an approach proposed for the synthesis of bicyclic 155 and spiro-compounds 156 and 157, which were used to synthesize enantiomerically pure clerodanes, which possess psychoactive properties, and drimane and lactarane sesquiterpenes, which are used in medicine [62,63]. Thus, 2 was used to synthesize the antibiotic aplasmomycin (142), which was isolated from a culture of the actinomycete Streptomyces griseus and is the sodium salt with empirical formula C 40 H 60 O 14 BNa (142) [57].…”

Section: Use Of 12-adducts Of Cyclic αβ-Enone Monoterpenoids and Ormentioning

confidence: 99%

Natural cyclic α, β-enone monoterpenoids in nucleophilic addition reactions

et al. 2006

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“…When a functionalized angular substitutent is present in the (natural) product that has to be synthesized, annelations of α-cyano ketones give good results 2 . The α-cyano group enhances the acidity of the α proton considerably with a minimum of extra steric hindrance.…”

Section: Introductionmentioning

confidence: 99%

Annelations of cyclic ß-cyanoketones in the synthesis of functionalized polycyclic compounds and steroids

Sobolev¹,

Vos²,

Zuilhof³

et al. 2005

Arkivoc

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Cyclic β-cyano ketones like cyanocarvone and 3-cyano-2-methylcyclopentanone can be annelated in high yields with methyl vinyl ketone, ethyl vinyl ketone and 6(3-methoxyphenyl)hex-1-en-3-one to cyano-substituted decalones and indanones. Computational studies at the B3LYP/6-31+G(d,p)//B3LYP/6-31G(d,p) level of theory show that thermodynamic rather than kinetic factors can explain the high yields. The annelated products are suitable intermediates for the synthesis of isoprenoid, steroid and homo steroid skeletons.

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Enantioselective Synthesis of Functionalised Decalones by Robinson Annulation of Substituted Cyclohexanones, Derived from R-(−)-Carvone

Cited by 29 publications

References 17 publications

Spirodionic Acid, a Novel Metabolite from Streptomyces sp., Part 2: Total Synthesis through a Twofold Michael Addition as a Selective Spiroannelation Strategy

Spirodionic Acid, a Novel Metabolite from Streptomyces sp., Part 2: Total Synthesis through a Twofold Michael Addition as a Selective Spiroannelation Strategy

Natural cyclic α, β-enone monoterpenoids in nucleophilic addition reactions

Annelations of cyclic ß-cyanoketones in the synthesis of functionalized polycyclic compounds and steroids

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