. Can. J. Chem. 57. 163 1 ( 1 979).(*)-Luciduline has been synthesised in seven steps from 2-(2-cyanoethy1)-5-methylcyclohex-2-en-1-one. The synthetic approach is adaptable to the synthesis of intermediates of interest in biosynthetic studies of the Lycopodium alkaloids. On a synthetise la (+)-luciduline en sept Ctapes a partir de la (cyano-2 ethyl)-2 methyl-5 cyclohex6ne-2 one-1. On pourrait adapter cette approche a la synth6se d'intermkdiaires interessants dans des etudes biosynthetiques des alcaloi'des du lycopodium.[Traduit par le journal]Luciduline (1) (originally designated L21) was The compound used as starting material in the first described by Manske and Marion (1) who synthesis was 2-(2-cyanoethy1)-5-methylcyclohex-2-isolated the alkaloid from Lycopodium lucidulurn en-1-one (5). This compound has recently been used Michx. Its structure was elucidated by Ayer et al. (2) by Heathcock et u I .~ in their synthesis of lycoby chemical degradation and by an X-ray study. podine. We have prepared it from 5-methyl-1,3-Luciduline is the only representative of this ring cyclohexanedione (6) using Clark and Heathcock's system that has been isolated from the Lyco-procedure (7) with slight modification. podiaceae.Two syntheses of luciduline have already been 0 reported, the first by Scott and Evans (3) and the second by Oppolzer and Petrzilka (4). Both syntheses lead in straightforward steps t o the stereochemically desired intermediates and eventually to the product. INeither however is related to the biosynthesis of the R alkaloid in the plant. The synthetic approach re-' LUcldU1ine 2 X = H 2 , R = H 3 R = HorCH, 4 X = O ; R = CzHs ported here is not biomimetic but leads t o an intermediate that may however be involved in the biosynthesis, not only of luciduline itself but also of other ring systems in this family of alkaloids (5).
gard the values presented in Table 1 as accurately measured at low temperature are depicted in Fig. 2. The representing the confornational thermodynamic computer program calculated the deviations in the slopes and the intercepts by standard statistical methods (9). parameters of the formyl group. ExperimentalCyclohexanecarboxaldehyde was purchased from Frinton Laboratories, South Vineland, New Jersey. Degassed 0.2 M solutions were employed.Spectra were recorded with a Varian XL-100-12 n.m.r. spectrometer equipped with a variable temperature probe. The temperatures were calibrated using a dummy n.m.r. tube containing a copper-constantan thermocouple and are believed to be accurate to f 2 OC.To ensure that non-saturating radiofrequency conditions were employed, spectra were initially recorded at widely different r.f. powers, and the relative peak areas were measured. Final conditions were then chosen where the slope of the relative peak area us. r.f. power graph was zero. Integration of the areas under the peaks was done by the cutting and weighing procedure. Each value represents an average of six determinations at a given temperature.Least squares analysis of the data was carried out with the aid of an XDS SIGMA 6 computer. Errors in -AGO were calculated from the equation AAGO = A A P + TAAS" + ATAS0. Contributions from the last term are negligibly small since AT is f 2 "C.The standard deviations in the equilibrium constants A new alkaloid (C30H4,N203S), isolated from Nuphar luteum, is shown to be neothiobinupharidine sulfoxide. The mass spectra of neothiobinupharidine and the new alkaloid are discussed.Un nouvel alcaloi'de (C30H42N203S), isole a partir du Nuphar lu/eum, s'est avtrt &tre le neothiobinupharidine sulfoxyde. Les spectres de masse du ntothiobinupharidine et du nouvel alcaloi'de sont discutts.Canadian Journal of Chemistry, 50, 1968Chemistry, 50, (1972 Several sulfur-containing alkaloids of Nuphar its structure was elucidated by X-ray analysis species have been described but for only one of (2). An isomer of 1, thiobinupharidine (3, 4), them, neothiobinupharidine (1) has the struc-is also known. Recently, two alkaloids related in ture and relative configuration been completely structure to 1 have been reported (5). The two resolved. Neothiobinupharidine was isolated alkaloids are bis-carbinolamines that on reducand studied in Poland (I) and some years later tion give dideoxy compounds, isomeric with one Can. J. Chem. Downloaded from www.nrcresearchpress.com by 54.213.204.173 on 05/10/18For personal use only.
Auf dem beschriebenen Weg können in befriedigenden Ausbeuten die Nuphar‐Alkaloide (VIIIa) und (VIIIb) erhalten werden.
The alkaloids (±)-nupharamine and (±)-3-epinupharamine were synthesized using 3-acetylfuran as the starting material. The conditions for stereoselective reduction of pyridine derivatives are described.
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