FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W1504263516> ?p ?o ?g. }

• W1504263516 abstract "This thesis presents a number of new applications of racemic and optically active sulfoximines to diastereoselective and asymmetric synthesis. In the first Chapter a review is made of the preparation of racemic and optically active sulfoximines and their applications to organic synthesis. The general aims of this project are presented. In Chapter two, our attempts to develop an asymmetric synthesis of the insect pheromone, Lardolure are presented. In the first step, the Michael addition reaction of lithiated N-tosyl 5-allyl 5-phenyl sulfoximine with 3-penten-2-one was undertaken. This reaction gave the 1,4-cc adduct with good diastereoselectivity (85 : 15). In the second step, the diastereoselective reduction of y-keto allylic sulfoximines with D I B A L H was explored. The stereochemistry of both the Michael adduct and the reduction products were determined by a combination of single crystal X-ray structural analysis and N M R spectroscopy. Further synthetic studies towards the preparation of Lardolure were not pursued since the desired Michael addition of the O -protected y-alcohol allylic sulfoximines with 3-penten-2-one did not occur. A novel palladium(O) catalysed rearrangement of primary and secondary allylic sulfoximines to their isomeric allylic sulfinamides, which upon subsequent base hydrolysis gave the corresponding TVprotected allylic amines, is reported in Chapter three. This facile rearrangement was shown to be highly efficient and regioselective. W h e n optically active secondary allylic sulfoximines were employed, these rearrangements resulted in the formation of chiral N-protected allylic amines in high enantiomeric purities. The mechanism and the stereochemical outcomes of these rearrangement reactions are also discussed. In Chapter four, the stereochemistry and diastereoselectivity of the Michael additions of oc-lithiated sulfoximines with enones under kinetically controlled conditions are reported. The initially formed anionic Michael adducts were found to undergo intramolecular displacement of the sulfonimidoyl group at rt to give cyclopropanes. The reactions of oc-lithiated sulfoximines with acyclic enones gave cyclopropanes in a highly efficient and diastereoselective manner. Optically active versions of these sulfoximines gave cyclopropanes in high enantiomeric purities. The absolute stereochemistries of the Michael adducts were determined from single crystal X-ray analysis and the stereochemistry of the cyclopropanes were determined by ID and 2D N M R spectroscopy. An one-pot method of preparation of bicyclo[2.2.1]heptanones and bicyclo[2.2.2]octanones via the Michael addition of five and six membered cyclic enones with lithiated 5-allyl 5-phenyl sulfone at rt was developed in Chapter five. W h e n acyclic enones were employed then novel 3-cyclohexen-l-ols were obtained. The stereochemistry of these annulation products was determined by single crystal X-ray structural analysis and N M R spectroscopy." @default.
• W1504263516 created "2016-06-24" @default.
• W1504263516 creator A5060673251 @default.
• W1504263516 date "1997-01-01" @default.
• W1504263516 modified "2023-09-27" @default.
• W1504263516 title "Diastereoselective and asymmetric synthesis via chiral sulfoximines" @default.
• W1504263516 cites W1506938930 @default.
• W1504263516 cites W1555195381 @default.
• W1504263516 cites W1605828942 @default.
• W1504263516 cites W1856523236 @default.
• W1504263516 cites W2094498700 @default.
• W1504263516 cites W624468233 @default.
• W1504263516 hasPublicationYear "1997" @default.
• W1504263516 type Work @default.
• W1504263516 sameAs 1504263516 @default.
• W1504263516 citedByCount "0" @default.
• W1504263516 crossrefType "journal-article" @default.
• W1504263516 hasAuthorship W1504263516A5060673251 @default.
• W1504263516 hasConcept C108204754 @default.
• W1504263516 hasConcept C120095180 @default.
• W1504263516 hasConcept C146686406 @default.
• W1504263516 hasConcept C161790260 @default.
• W1504263516 hasConcept C178790620 @default.
• W1504263516 hasConcept C185592680 @default.
• W1504263516 hasConcept C3019471444 @default.
• W1504263516 hasConcept C3141732 @default.
• W1504263516 hasConcept C486523 @default.
• W1504263516 hasConcept C59759590 @default.
• W1504263516 hasConcept C71240020 @default.
• W1504263516 hasConceptScore W1504263516C108204754 @default.
• W1504263516 hasConceptScore W1504263516C120095180 @default.
• W1504263516 hasConceptScore W1504263516C146686406 @default.
• W1504263516 hasConceptScore W1504263516C161790260 @default.
• W1504263516 hasConceptScore W1504263516C178790620 @default.
• W1504263516 hasConceptScore W1504263516C185592680 @default.
• W1504263516 hasConceptScore W1504263516C3019471444 @default.
• W1504263516 hasConceptScore W1504263516C3141732 @default.
• W1504263516 hasConceptScore W1504263516C486523 @default.
• W1504263516 hasConceptScore W1504263516C59759590 @default.
• W1504263516 hasConceptScore W1504263516C71240020 @default.
• W1504263516 hasLocation W15042635161 @default.
• W1504263516 hasOpenAccess W1504263516 @default.
• W1504263516 hasPrimaryLocation W15042635161 @default.
• W1504263516 hasRelatedWork W1997556832 @default.
• W1504263516 hasRelatedWork W2094248924 @default.
• W1504263516 hasRelatedWork W2145425768 @default.
• W1504263516 hasRelatedWork W2149744622 @default.
• W1504263516 hasRelatedWork W2949167369 @default.
• W1504263516 hasRelatedWork W2950166035 @default.
• W1504263516 hasRelatedWork W2950383256 @default.
• W1504263516 hasRelatedWork W2950452256 @default.
• W1504263516 hasRelatedWork W2950570305 @default.
• W1504263516 hasRelatedWork W2951776596 @default.
• W1504263516 hasRelatedWork W2952400263 @default.
• W1504263516 hasRelatedWork W2952519021 @default.
• W1504263516 hasRelatedWork W2953390152 @default.
• W1504263516 hasRelatedWork W2954904469 @default.
• W1504263516 hasRelatedWork W2972132968 @default.
• W1504263516 hasRelatedWork W3017258310 @default.
• W1504263516 hasRelatedWork W3042076142 @default.
• W1504263516 hasRelatedWork W3118432843 @default.
• W1504263516 hasRelatedWork W3139436110 @default.
• W1504263516 hasRelatedWork W3143532597 @default.
• W1504263516 isParatext "false" @default.
• W1504263516 isRetracted "false" @default.
• W1504263516 magId "1504263516" @default.
• W1504263516 workType "article" @default.