Asymmetric Intramolecular Diels-Alder Reaction Research Articles

H-Bonding Mediated Asymmetric Intramolecular Diels-Alder Reaction in the Formal Synthesis of (+)-Aplykurodinone-1.

An asymmetric formal total synthesis of (+)-aplykurodinone-1 was achieved using a route, in which hydrogen bonding serves as a stereochemical control element governing the π-facial selectivity of intramolecular Diels-Alder (IMDA) reaction of an enone tethered 2-pyrone. In the IMDA process, the configuration at a stereogenic, hydroxyl bearing an α-carbon in the enone dienophile is conveyed in a highly effective manner through intramolecular hydrogen bonding with the enone carbonyl oxygen. The tricyclic lactone, generated in this process, was successfully converted to a late stage intermediate in Danishefsky's synthesis of aplykurodinone-1.

Application of Carbohydrate-Templated Asymmetric Diels-Alder Reaction to the Syntheses of ent-Penicillones A and B.

Total syntheses of ent-penicillones A (ent-1) and B (ent-2) from 3,5-dimethylcatechol (3) were accomplished in 10 and 9 synthetic steps, respectively. A carbohydrate-templated asymmetric intramolecular Diels-Alder reaction of a masked o-benzoquinone (MOB) 9 and an aqueous acid-catalyzed intramolecular aldol reaction are the key synthetic steps. In addition, the absolute configurations of the bicyclo[2.2.2]oct-5-en-2-one core obtained from the per-O-benzylated α-d-glucopyranosyl as a carbohydrate template in the intramolecular Diels-Alder reaction of MOBs were revised.

Asymmetric Intramolecular Diels-Alder Reactions Catalyzed by Ruthenium

Asymmetric Intramolecular Diels-Alder Reactions Catalyzed by Ruthenium

Intramolecular Diels–Alder reactions using chiral ruthenium Lewis acids and application in the total synthesis of ent-ledol

One-point binding chiral ruthenium Lewis acids incorporating the C(2)-symmetric electron-poor bidentate phosphinite ligand BIPHOP-F and a Cp or an indenyl 'roof' can efficiently catalyze asymmetric intramolecular Diels-Alder reactions of trienes to form bicyclic adducts with good to excellent asymmetric induction. This reaction forms the key step in a total synthesis of ent-ledol in 96% ee. The synthesis also helps to clarify the stereochemical assignment of ledol and inconsistencies in the measured optical rotation.

ChemInform Abstract: Asymmetric Synthesis of the Hydronaphthalene Moieties of Mevinic Acids.

Abstract The hydronaphthalene moieties of mevinic acids are synthesized enantioselectively by using the asymmetric intramolecular Diels-Alder reaction catalyzed by a chiral titanium reagent.

Studies on a Total Synthesis of Plakotenin: Synthesis of Optically Active trans-Hydrindanes by Diastereoselective Asymmetric Intramolecular Diels-Alder Reaction

Studies on a Total Synthesis of Plakotenin: Synthesis of Optically Active trans-Hydrindanes by Diastereoselective Asymmetric Intramolecular Diels-Alder Reaction

Configurations of Cycloadducts Formed in Asymmetric Intramolecular Diels–Alder Reactions

Intramolecular cycloaddition reactions of two furfuryl fumarates yield, after crystallization, pure diastereomers of oxabicyclo[2.2.1]heptene derivatives which are versatile starting points for the total synthesis of natural products. The crystal structures of the adducts, menthyl (3aS,6R,7R,7aR)-1,3,3a,6,7,7a-hexahydro-3,3-dimethyl-1-oxo-3a,6-epoxyisobenzofuran-7-carboxylate, C 21 H 30 O5, and methyl syn-3-tert-butyl-1,3,3a,6,7,7a-hexahydro-1-oxo-3a,6-epoxyisobenzofuran-7-carboxylate, C 14 H 18 O 5 , establish the configuration at the chiral centers and provide insights into the factors controlling the diastereomeric differentiation.

Asymmetric intramolecular Diels-Alder reactions of sulfoximine-activated trienes

A series of N-substituted sulfoximidoyl-1,6,8-nonatrienes and 1,7,9-decatrienes were synthesised and subjected to thermal intramolecular Diels-Alder (IMDA) reactions to give diastereomeric mixtures of substituted bicyclo[4.3.0]nonanes and -[4.4.0]decanes. The reactions showed varying selectivities. Endo/exo selectivity was interpreted in terms of a combination of steric factors and the asynchronous nature of the cycloadditions. Diastereofacial selectivity could be rationalised by considering attack by the diene on the less hindered face of the conformationally extended vinylic sulfoximine dienophile.

Enantiogenic total syntheses of (-)-indolizidines (bicyclic gephyrotoxins) 205A, 207A, 209B, and 235B via the intramolecular Diels-Alder reaction of a chiral N-acylnitroso compound

A general protocol for the enantiogenic total syntheses of a series of the 5-substituted 8-methylindolizidine class of alkaloids from the arrow poison frog, i.e., (-)-indolizidines 205A (1), 207A (2), 209B (3), and 235B (4), is described, in which a key step is the asymmetric intramolecular Diels-Alder reaction of the chiral N-acylnitroso compound 8 leading to the bicyclic oxazinolactam 7 which was utilized as a versatile common chiral intermediate for the preparation of these alkaloids

The total synthesis of (?)-indolizidines 205A and 235B

The total synthesis of (–)-indolizidines 205A and 235B, alkaloids from the arrow poison-frog, via a common chiral oxazino-lactam, prepared by an asymmetric intramolecular Diels–Alder reaction of an N-acylnitroso intermediate, is described.

Asymmetric synthesis of the hydronaphthalene moieties of mevinic acids

The hydronaphthalene moieties of mevinic acids are synthesized enantioselectively by using the asymmetric intramolecular Diels-Alder reaction catalyzed by a chiral titanium reagent.

Asymmetric Intramolecular Diels–Alder Reaction Catalyzed by the Chiral Titanium Reagent

Abstract The highly enantioselective intramolecular Diels–Alder reaction is achieved using a catalytic amount of the chiral titanium reagent prepared from TiCl2(OPri)2 and the tartrate derived chiral 1,4-diol.

Asymmetric intramolecular Diels-Alder reaction catalyzed by chiral acyloxyborane complex

Intramolecular Diels-Alder reaction of 2-methyl-(E,E)-2,7,9-decatrienal catalyzed by chiral acyloxyborane complex proceeds with high stereo and enantioselectivities.

Enantioselective synthesis and absolute configuration of (−)-pulo'upone by asymmetric intramolecular diels-alder reaction

(−)-Pulo'upone ( 1 ) was synthesized via an asymmetric, bornane-10,2-sultam- directed, intramolecular Diels- Alder reaction ( 3 → 2 ) and a 2-pyridylcuprate/allylacetate coupling ( 18 → 1 ). The ( 6'R, 9'S, 13'R, 14'R)- configuration of (−)- 1 follows from an X-ray diffraction analysis of the cycloaddition product 2 .

Asymmetric synthesis of trans-benzoperhydroindan: asymmetric induction in intramolecular Diels–Alder reactions of o-quinodimethanes

Diastereofacial selection has been shown to occur in the asymmetric intramolecular Diels–Alder reactions of chiral o-quinodimethanes generated by thermal ring-opening of the chiral benzocyclobutenes (1a,b,e,f).

ChemInform Abstract: Asymmetric Intramolecular Diels‐Alder Reactions of N‐Acyl‐camphorsultam Trienes.

Chemischer InformationsdienstVolume 17, Issue 10 Preparative Organic Chemistry ChemInform Abstract: Asymmetric Intramolecular Diels-Alder Reactions of N-Acyl-camphorsultam Trienes. W. OPPOLZER, W. OPPOLZERSearch for more papers by this authorD. DUPUIS, D. DUPUISSearch for more papers by this author W. OPPOLZER, W. OPPOLZERSearch for more papers by this authorD. DUPUIS, D. DUPUISSearch for more papers by this author First published: March 11, 1986 https://doi.org/10.1002/chin.198610118AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue10March 11, 1986 RelatedInformation

コンパクチン（ＭＬ‐２３６Ｂ）およびモナコリンＫ（メビノリン）の全合成

Convergent and enantiospecific syntheses of compactin (1 a) and mevinolin (1 b), potent competitive inhibitor of HMG-CoA reductase, have been achieved via asymmetric intramolecular Diels-Alder reaction of acyclic (E, E, E) -trienone 4 leading to trans-octalone 3, a common intermediate for congeners. Chirality of C13 in 4 was designed to induce the four asymmetric centers with desired configuration by this reaction : the chirality controlled the approach of the dienophile from a single diastereotopic face. Trienone 4 was expeditiously constructed by the combination of two segments 5 and 6. Enantio- and stereo-specific synthesis of 6, a chiral 1, 3, 5- triol derivative, rested on the two novel methodologies, i.e, the convenient asymmetric reduction of β-keto carboxylate 19 d with baker's yeast and the regio- and stereo-selective iodofunctionalization (1, 3-asymmetric induction) of homoallylic carbamate. Preparation of 5 in its optically active form was accomplished by the elaboration of readily available γ-lactone 12.

ChemInform Abstract: THE ASYMMETRIC DIELS‐ALDER REACTIONS OF α,β‐UNSATURATED CARBOXYLIC AMIDES DERIVED FROM (‐)‐PHENYLGLYCINOL AND THE ASYMMETRIC TOTAL SYNTHESIS OF (+)‐FARNESIFEROL C

AbstractDie intramolekulare Diels‐Alder‐Reaktion der Furfurylacrylamide (I) liefert die cis‐trans‐isomeren Cycloaddukte (II) und (III), von denen die Verbindung (IIa) wie im Formelschema angegeben zum Farnesiferol (XIV) umgesetzt wird.

THE ASYMMETRIC DIELS–ALDER REACTIONS OF α,β-UNSATURATED CARBOXYLIC AMIDES DERIVED FROM (−)-PHENYLGLYCINOL AND THE ASYMMETRIC TOTAL SYNTHESIS OF (+)-FARNESIFEROL C

Abstract The asymmetric intramolecular Diels–Alder reactions of α,β-unsaturated carboxylic amides derived from (−)-phenylglycinol were studied and successfully applied to the asymmetric total synthesis of (+)-farnesiferol C.