Abstract:Die Ketoester (I) lassen sich mit den Chloracylchloriden (II) (analog auch mit entsprechenden α‐Acetoxy‐acylchloriden) in Gegenwart "von Mg‐äthylat in Benzol bei 10°C zu den Äthoxycarbonyldihydrofuranonen (III) umsetzen.
“…Ideally, it would be suitable to provide not only (+)‐gregatin B [(+)‐( R )‐ 1c ] but also the third‐generation structures 2c – 10c of the other members of the gregatin/aspertetronin family. A whole array of existing 3(2 H )‐furanone approaches40–47 held little promise for such a strategy. In contrast, the γ‐acyloxy‐β‐oxo ester 43 had been reported to give type‐ c furanone 40 upon exposure to basic methanol (Scheme ) 48.…”
Section: Syntheses Of the Natural Enantiomers Of Gregatin A Gregatinmentioning
Comprehensive comparisons of 1H and 13C NMR chemical shift values in the furanone cores a, b, and c provide plausible support for a reassessment of the furanone nuclei of the title compounds from b to c. Total syntheses via enantiomerically pure lactic esters were based on the Seebach–Fráter “self‐reproduction of stereocenters” methodology. Attachment of the hexadienyl side‐chain in a trans,trans‐selective manner was achieved by addition of the Seebach–Fráter enolate to trans‐hex‐4‐en‐1‐al rather than to trans‐hex‐3‐en‐1‐al. The type‐c furanone cores of the synthetic materials were reached by single or double acylation of a model γ‐hydroxy‐β‐oxo ester (compound 50) and its hexadiene‐containing counterpart 29. Our syntheses confirmed the novel connectivities in six compounds. In addition, they required revision of the configuration of a quaternary carbon atom in five cases. Moreover, they allowed elucidation of the configurations of four previously unassigned stereocenters. Hindsight analyses of why the furanone cores of the title compounds had been misinterpreted as a and/or b instead of c are given. Why the stereocenters in the heterocycles had been incorrectly configured, on the bases (a) of relay studies in the 1960s, and (b) of a 1984 total synthesis of gregatin B, is also discussed.
“…Ideally, it would be suitable to provide not only (+)‐gregatin B [(+)‐( R )‐ 1c ] but also the third‐generation structures 2c – 10c of the other members of the gregatin/aspertetronin family. A whole array of existing 3(2 H )‐furanone approaches40–47 held little promise for such a strategy. In contrast, the γ‐acyloxy‐β‐oxo ester 43 had been reported to give type‐ c furanone 40 upon exposure to basic methanol (Scheme ) 48.…”
Section: Syntheses Of the Natural Enantiomers Of Gregatin A Gregatinmentioning
Comprehensive comparisons of 1H and 13C NMR chemical shift values in the furanone cores a, b, and c provide plausible support for a reassessment of the furanone nuclei of the title compounds from b to c. Total syntheses via enantiomerically pure lactic esters were based on the Seebach–Fráter “self‐reproduction of stereocenters” methodology. Attachment of the hexadienyl side‐chain in a trans,trans‐selective manner was achieved by addition of the Seebach–Fráter enolate to trans‐hex‐4‐en‐1‐al rather than to trans‐hex‐3‐en‐1‐al. The type‐c furanone cores of the synthetic materials were reached by single or double acylation of a model γ‐hydroxy‐β‐oxo ester (compound 50) and its hexadiene‐containing counterpart 29. Our syntheses confirmed the novel connectivities in six compounds. In addition, they required revision of the configuration of a quaternary carbon atom in five cases. Moreover, they allowed elucidation of the configurations of four previously unassigned stereocenters. Hindsight analyses of why the furanone cores of the title compounds had been misinterpreted as a and/or b instead of c are given. Why the stereocenters in the heterocycles had been incorrectly configured, on the bases (a) of relay studies in the 1960s, and (b) of a 1984 total synthesis of gregatin B, is also discussed.
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