FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2952303611> ?p ?o ?g. }

• W2952303611 endingPage "6209" @default.
• W2952303611 startingPage "6195" @default.
• W2952303611 abstract "The development of an effective chiral auxiliary for hydroxyalkyl radicals is delineated. Both the 2-tetrahydropyranyl (THP) and tri-O-benzyl-2-deoxy-α-d-glucopyranosyl (GLU) auxiliaries resulted in diastereoselective radical additions to methyl acrylate at −78 °C (ds = 6/1 and 11/1, respectively). The developing stereochemistry at the radical center was completely under auxiliary control. Correlation experiments showed that the d-GLU auxiliary led to attack on the radical Si-face. The selectivity of these radical additions dropped-off considerably when the more reactive 2-nitropropene trap was employed. Computational studies suggested that the observed facial selectivity was due primarily to entropic factors in the transition state but that a smaller temperature-dependent enthalpic contribution was also involved. It was hypothesized that incorporation of a quaternary center at C-6 (THP numbering) would restore the facial selectivity with more reactive radical traps by restricting the orientations available to the incoming alkene. In the event, the trans-6-tert-butyltetrahydropyranyl (tBu-THP) auxiliary resulted in very good diastereoselection with 2-nitropropene (ds = 35/1 at −78 °C, 15/1 at 0 °C, and 8/1 at RT) as did the tri-O-benzyl-6,6-dimethyl-2-α-d-deoxyglucopyranosyl (diMe-GLU) auxiliary during additions to ethyl α-trifluoroacetoxyacrylate (ds = 10/1 at 0 °C). A protocol for recovery of the sugar-derived chiral auxiliaries was also established. This work sets the stage for the development of a novel approach to 1, 3, 5...(2n + 1) polyols based on iterative radical homologation as well as the application of these pyranosidic auxiliaries to other synthetically important reactions." @default.
• W2952303611 created "2019-06-27" @default.
• W2952303611 creator A5002571394 @default.
• W2952303611 creator A5037161663 @default.
• W2952303611 creator A5059058058 @default.
• W2952303611 creator A5060098801 @default.
• W2952303611 creator A5064074234 @default.
• W2952303611 creator A5087436993 @default.
• W2952303611 date "2002-07-25" @default.
• W2952303611 modified "2023-09-30" @default.
• W2952303611 title "Development of an Effective Chiral Auxiliary for Hydroxyalkyl Radicals" @default.
• W2952303611 cites W1514707562 @default.
• W2952303611 cites W1966030543 @default.
• W2952303611 cites W1983812813 @default.
• W2952303611 cites W1985067345 @default.
• W2952303611 cites W1986953443 @default.
• W2952303611 cites W1991680603 @default.
• W2952303611 cites W1994062897 @default.
• W2952303611 cites W1999798195 @default.
• W2952303611 cites W2010615937 @default.
• W2952303611 cites W2013687966 @default.
• W2952303611 cites W2024834377 @default.
• W2952303611 cites W2033600113 @default.
• W2952303611 cites W2036496103 @default.
• W2952303611 cites W2040198500 @default.
• W2952303611 cites W2043966259 @default.
• W2952303611 cites W2059969255 @default.
• W2952303611 cites W2060554135 @default.
• W2952303611 cites W2063617976 @default.
• W2952303611 cites W2067559820 @default.
• W2952303611 cites W2069275723 @default.
• W2952303611 cites W2077013947 @default.
• W2952303611 cites W2081191918 @default.
• W2952303611 cites W2082939750 @default.
• W2952303611 cites W2083618237 @default.
• W2952303611 cites W2085445136 @default.
• W2952303611 cites W2090591453 @default.
• W2952303611 cites W2091342046 @default.
• W2952303611 cites W2116588080 @default.
• W2952303611 cites W2135526107 @default.
• W2952303611 cites W2162035314 @default.
• W2952303611 cites W2315574817 @default.
• W2952303611 cites W2949446606 @default.
• W2952303611 cites W2949545694 @default.
• W2952303611 cites W2949703300 @default.
• W2952303611 cites W2950125327 @default.
• W2952303611 cites W2950303105 @default.
• W2952303611 cites W2950332777 @default.
• W2952303611 cites W2950361981 @default.
• W2952303611 cites W2952340552 @default.
• W2952303611 cites W3025623913 @default.
• W2952303611 cites W4236853794 @default.
• W2952303611 cites W4251500918 @default.
• W2952303611 cites W612383473 @default.
• W2952303611 doi "https://doi.org/10.1021/jo010880f" @default.
• W2952303611 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/12182661" @default.
• W2952303611 hasPublicationYear "2002" @default.
• W2952303611 type Work @default.
• W2952303611 sameAs 2952303611 @default.
• W2952303611 citedByCount "23" @default.
• W2952303611 countsByYear W29523036112012 @default.
• W2952303611 countsByYear W29523036112013 @default.
• W2952303611 countsByYear W29523036112014 @default.
• W2952303611 countsByYear W29523036112021 @default.
• W2952303611 crossrefType "journal-article" @default.
• W2952303611 hasAuthorship W2952303611A5002571394 @default.
• W2952303611 hasAuthorship W2952303611A5037161663 @default.
• W2952303611 hasAuthorship W2952303611A5059058058 @default.
• W2952303611 hasAuthorship W2952303611A5060098801 @default.
• W2952303611 hasAuthorship W2952303611A5064074234 @default.
• W2952303611 hasAuthorship W2952303611A5087436993 @default.
• W2952303611 hasConcept C118792377 @default.
• W2952303611 hasConcept C139066938 @default.
• W2952303611 hasConcept C146686406 @default.
• W2952303611 hasConcept C155647269 @default.
• W2952303611 hasConcept C161790260 @default.
• W2952303611 hasConcept C178790620 @default.
• W2952303611 hasConcept C185592680 @default.
• W2952303611 hasConcept C2776254738 @default.
• W2952303611 hasConcept C2779061078 @default.
• W2952303611 hasConcept C71240020 @default.
• W2952303611 hasConceptScore W2952303611C118792377 @default.
• W2952303611 hasConceptScore W2952303611C139066938 @default.
• W2952303611 hasConceptScore W2952303611C146686406 @default.
• W2952303611 hasConceptScore W2952303611C155647269 @default.
• W2952303611 hasConceptScore W2952303611C161790260 @default.
• W2952303611 hasConceptScore W2952303611C178790620 @default.
• W2952303611 hasConceptScore W2952303611C185592680 @default.
• W2952303611 hasConceptScore W2952303611C2776254738 @default.
• W2952303611 hasConceptScore W2952303611C2779061078 @default.
• W2952303611 hasConceptScore W2952303611C71240020 @default.
• W2952303611 hasIssue "17" @default.
• W2952303611 hasLocation W29523036111 @default.
• W2952303611 hasLocation W29523036112 @default.
• W2952303611 hasOpenAccess W2952303611 @default.
• W2952303611 hasPrimaryLocation W29523036111 @default.
• W2952303611 hasRelatedWork W1969404129 @default.
• W2952303611 hasRelatedWork W2061908415 @default.

• next