A model for asymmetric induction in the Diels-Alder reaction

Trost, Barry M.; Okrongly, David; Belletire, J. L.

doi:10.1021/ja00545a049

Cited by 153 publications

(24 citation statements)

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“…Indeed, a single product emerges whose absolute configuration conforms to this prediction (Eq. 27) (37). Use of such weak secondary interactions has had remarkable success in related thermal processes (39,40).…”

Section: Enantioselectivitymentioning

confidence: 99%

“…As already -89 33 ( To a large extent, progress in the development of an asymmetric process has more successful one is to convert enantioselectivity into diastereoselectivity, the chiral inducing agent becoming covalently bonded to the substrate in such a fashion that it can be subsequently cleaved. The Diels-Alder reaction is an excellent framework with which to explore such possibilities since many chiral centers are created from two normally achiral starting materials (37)(38)(39). Interaction of a phenyl ring with the IT-system of a dienophile or a diene (a so-called irstacking interaction) can induce cycloaddition to occur preferentially to one of the two enantiotopic (or, in reality, diastereotopic) faces of these reacting part- …”

Section: Enantioselectivitymentioning

confidence: 99%

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Selectivity: A Key to Synthetic Efficiency

Trost

1983

Science

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299

231

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The efficient synthesis of organic compounds requires the development of processes with enhanced selectivity. Selectivity is categorized according to chemical reactivity (chemoselectivity), orientation (regioselectivity), and spatial arrangement (diastereoselectivity and enantioselectivity). Recent developments in reduction-oxidation methods and C-C bond forming reactions illustrate some solutions to problems of selectivity. The design of selectivity-inducing groups and the increased role of main group and transition metals in enhancing selectivity are especially noted.

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Section: Enantioselectivitymentioning

confidence: 99%

Section: Enantioselectivitymentioning

confidence: 99%

Selectivity: A Key to Synthetic Efficiency

Trost

1983

Science

Self Cite

299

231

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“…It was initially proposed that a p-stacking interaction was taking place between the diene and the aromatic nucleus, shielding one of the faces of the diene when under its cisoid conformation ( Figure 3). 67 This hypothesis was elegantly substantiated by preparing the 1,4-disubstituted butadiene, which turned out to be inert, as sandwiched between the two asymmetric units. However, the p-stacking model was soon challenged, and a conformation in which the phenyl oriented perpendicular to the diene plane ( Figure 3) was held responsible for the diastereoselectivity.…”

Section: Scheme 16mentioning

confidence: 99%

Selectivity Controls in the [4+2] Cycloadditions of 1-Oxygenated Dienes

Maddaluno¹

2006

Synlett

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“…Such intermediates typically undergo Diels-Alder reactions in the presence of a Lewis acid catalyst with diastereoselection exceeding 90% (for example, see ref. 25). They are devised in such a way that the chiral auxiliary group effectively blocks the Re face of the dienophile or diene and this induces high diastereofacial selectivity.…”

Section: Introductionmentioning

confidence: 99%

Facial selective Diels–Alder reactions of (1R,5R)-(+)-3-carbomethoxy-6,6-dimethylbicyclo[3.1.1]hept-3-en2-one. Unusual ketalization–fragmentation reaction of adducts

Liu¹,

Chew²,

Browne³

et al. 1994

Can. J. Chem.

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The stereofacially differentiated enone ester 5 has been used to study the effects of steric influence on the Diels-Alder reaction. In general, under Lewis acid catalysis, 5 adds to dienes at low to ambient temperatures in a reasonable rate. Yields of predictable chiral adducts are moderate with the unexpected exception of zinc chloride catalyzed reactions, which provide good to high yields. In all cases only products of addition to the Si face of general type 21 were observed. The regiochemistry of the adducts is exclusively that predicted by the ortho and para rules. The stereochemistry shows a high selectivity in favor of ester-endo transition state products. Rationales for the observed stereoselectivities are discussed. The fragmentation of adducts of 5, in particular keto ester 9, has been briefly examined. Olefins 30 and 46 derived from 9 have been converted to ring-opened cadinane skeletons 31 and 47, respectively, by conditions we have previously reported. In an entirely new and unexpected reaction, simultaneous ketalization and fragmentation of the cyclobutane ring of ketones derived from 9 gave ring-opened ketals 34 + 35 (from 29), 36 + 37 (from 9), 39 (from 38) and 42 + 43 (from 40).HSING-JANG LIU, SEW YEU CHEW, ERIC N.C. BROWNE et JEUNG BEA KIM. Can. J. Chem. 72, 1193Chem. 72, (1994.On a utilisC 1'Cnone ester 5 stCrCofacialement diffCrenciC pour Ctudier les effets stCriques sur la rCaction de Diels-Alder. En gCnCral, dans des conditions de catalyse acide de Lewis, le composC 5 s'additionne aux dibnes a des vitesses raisonnables, des tempkratures ne dCpassant pas la tempkrature ambiante. Les rendements des adduits chiraux attendus sont modCrCs, a l'exception notable des rkactions catalysCes par le chlorure de zinc qui donnent des rendements allant de bons 5 excellents. Dans tous les cas, on n'observe que les produits d'addition sur la face Si, de type gCnCral21. La rtgiochimie des produits est exclusivement celle que l'on peut prCdire sur la base des rbgles ortho etpara. La stCrCochimie prksente une grande sClectivitC pour les produits formCs par le biais de 1'Ctat de transition endo de l'ester. On a examink bribvement la fragmentation des adduits du produit 5, en particulier le cCto ester 9. Utilisant des conditions rapportCes antkrieurement, on a transform6 les olkfines 30 et 46, provenant du produit 9, en squelettes des cadinanes 2 cycle ouvert 31 et 47 respectivement. Par une rCaction aussi nouvelle qu'inattendue, une cktalisation et une fragmentation simultanCe du noyau cyclobutane des cCtones dCrivCs du produit 9 ont fourni les cCtals a cycles ouverts 34 + 35 (ii partir de 29), 36 + 37 (ii partir de 9), 39 (a partir de 38) et 42 + 43 (a partir de 40).[Traduit par la RCdaction]

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A model for asymmetric induction in the Diels-Alder reaction

Cited by 153 publications

References 0 publications

Selectivity: A Key to Synthetic Efficiency

Selectivity: A Key to Synthetic Efficiency

Selectivity Controls in the [4+2] Cycloadditions of 1-Oxygenated Dienes

Facial selective Diels–Alder reactions of (1R,5R)-(+)-3-carbomethoxy-6,6-dimethylbicyclo[3.1.1]hept-3-en2-one. Unusual ketalization–fragmentation reaction of adducts

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