A Short Synthesis of (±)-13-Deoxyserratine

Cassayre, Jérôme; Gagosz, Fabien; Zard, Samir Z.

doi:10.1002/1521-3773(20020517)41:10<1783::aid-anie1783>3.0.co;2-i

Cited by 107 publications

(34 citation statements)

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“…After the reaction mixture was stirred at 0°C for 8.5 h, it was poured into ice-cold water and was extracted with 5% MeOH in CHCl 3 . The combined organic phase was washed with brine, dried over MgSO 4 Partial Acetylation of Deacetyllycoclavine (15) To a solution of 15 (9.4 mg, 0.0355 mmol) in dry CH 2 Cl 2 (0.5 ml) was added dry Ac 2 O (3.3 ml, 0.0355 mmol) and dry pyridine (28 ml, 0.173 mmol) at 0°C under argon atmosphere. After the reaction mixture was stirred at room temperature for 20.5 h, it was warmed to 40°C and stirred for further 97.5 h. Then the reaction mixture was cooled to room temperature and evaporated to dryness.…”

Section: Hydrolysis Of Enol Acetate (14)mentioning

confidence: 99%

“…NaHCO 3 solution and was extracted with 5% MeOH in CHCl 3 . The combined organic phase was dried over MgSO 4 35 H 46 NO 6 576.3325). A solution of the ester (9.4 mg, 0.016 mmol) in dry EtOH (0.5 ml) was hydrogenated in the presence of 10% Pd on carbon (4.6 mg) for 1 h at room temperature.…”

Section: Hydrolysis Of Enol Acetate (14)mentioning

confidence: 99%

“…Lycopodium alkaloids [1][2][3] isolated from club mosses of the genus Lycopodium (Lycopodiaceae) exhibit fascinating complex structures and have attracted the attention of synthetic organic chemists [4][5][6][7][8][9][10] as well as pharmacologists because of such potent biological activities as an inhibitory effect on acetylcholinesterase. 11) Recent extensive studies on the chemical constituents in Lycopodium plants have resulted in the isolation of a number of new alkaloids having novel and diverse structures.…”

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confidence: 99%

“…High-resolution fast atom bombardment mass spectrometry (HR-FAB-MS) analysis gave m/z 296.1848 (MϩH) ϩ (D Ϫ1.4 mmu) and established the molecular formula as C 16 H 25 NO 4 . IR absorption implied the presence of hydroxyl (3403 cm…”

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Ten New Lycopodium Alkaloids Having the Lycopodane Skeleton Isolated from Lycopodium serratum THUNB.

et al. 2003

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(10), having lycopodine-related structures, were isolated from the club moss Lycopodium serratum THUNB. and their structures were elucidated on the basis of spectroscopic analysis and/or chemical transformation.Key words alkaloid; Lycopodium; structure elucidation; X-ray crystal structure; NMR; chemical transformation Lycoposerramine-G (2) was obtained as a colorless amorphous powder. HR-FAB-MS analysis gave m/z 280.1893 (MϩH) ϩ (D Ϫ2.0 mmu) and established the molecular formula as C 16 H 25 NO 3 , which was one oxygen atom less than 1 described above. The 1 H-and 13 C-NMR (Table 1) spectra of 2, which resembled those of 1 except for the chemical shifts of the carbons adjacent to nitrogen, indicated that 1 was an N-oxide derivative of 2. Actually, when 2 was treated with one equivalent of m-CPBA, lycoposerramine-F (1) was obtained in 63% yield, thereby establishing the structure of the new alkaloid as formula 2.Lycoposerramine-H (3) was obtained as colorless prisms (mp 227-228°C, sublimation). HR-FAB-MS analysis gave m/z 262.1809 (MϩH) ϩ (D ϩ0.2 mmu) and established the molecular formula as C 16 H 23 NO 2 , which indicated that 3 had one extra unsaturated number compared to common lycopodine-type alkaloids.1 H-and 13 C-NMR spectra (see Table 1) as well as DEPT spectra suggested the presence of one ketone, a trisubstituted olefin bearing a methyl group, one sp 3 quaternary carbon, four sp 3 methines (one of which had a hydroxyl function), and seven sp 3 methylenes. 1 H-1 H COSY and HMQC spectra revealed connectivities as shown by the bold line in Fig. 3. Further, allyl couplings between the olefinic proton (d 5.35, H-8) and methyl protons (d 1.58, H-16) and methylene protons (d 1.98, 2.70, H-14), as well as homoallyl coupling between the methyl protons (H-16) and the methine proton (d 2.52, H-7), indicated the presence of a double bond at the C-8 (d 121.6)-C-15 (d 135.9) position of the lycopodine skeleton. The location of the secondary hydroxyl group was inferred from the HMBC cross-peaks between the proton at d 3.78 (d, Jϭ2.7 Hz) and the carbonyl carbon (d 212.4, C-5) and the methine carbon at d 38.7 (C-4). The structure including the stereochemistry of the secondary hydroxyl group at C-6 was determined by X-ray analysis as formula 3 (Fig. 3). This is the first example of a lycopodine-type alkaloid that has a double bond at the C-8-C-15 position.Lycoposerramine-I (4) showed a molecular ion peak at m/z 261 and the molecular formula, C 16 H 23 NO 2 , which was established by HR-FAB-MS [m/z 262.1802 (MϩH) ϩ , D Ϫ0.5 mmu], was identical with that of 3 described above. Comparison of its1 H-and 13 C-NMR spectra (see Table 1) with those of 3 suggested that the two alkaloids were isomers at the position of the secondary hydroxyl group. The chemical shifts at C-10 (d 35.5), C-11 (d 69.2), and C-12 (d 44.6) in 4 as well as the HMBC cross-peak (Fig. 4) between the low-field proton (d 4.34) and the quaternary carbon at C-13 (d 59.7) indicated that the hydroxyl group existed at the C-11 position. The stereochemistry...

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Section: Hydrolysis Of Enol Acetate (14)mentioning

confidence: 99%

Section: Hydrolysis Of Enol Acetate (14)mentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Ten New Lycopodium Alkaloids Having the Lycopodane Skeleton Isolated from Lycopodium serratum THUNB.

et al. 2003

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“…These unique skeletons have also been challenging targets for total synthesis. [4][5][6][7][8] Among them, huperzine A is a highly specific and potent inhibitor of acetylcholinesterase (AChE).…”

Section: Notesmentioning

confidence: 99%