Synthesis of (4,8,2,3,2'--2'-hydroxyhexadecanoyl-1--β-D-glucopyranosyl-9-methyl-4,8-sphingadienine, the fruiting-inducing cerebroside in a basidiomycete

Isolation and Structure of Four New Ceramides from the Starfish Luidia maculata

“…Furthermore, LMCer-1 was thought to possess normal and ante-iso 8) type side chains since the carbon signals for the terminal methyl groups were observed at d C ϭ14.2 (normal) and d C ϭ11.4, 19.2 (ante-iso) in the 13 C-NMR (Table 1). The 1 H-NMR signals of the basic structure of LMCer-1 were in good agreement with those of known synthetic ceramide 1b, 9) which is composed of (2S,3R,4E)-sphingosine and (R)-2-hydroxy fatty acid. The above fact and the optical rotation of the LMCer-1 series, LMCer-1-1 (ϩ3.3) (vide infra) and the synthetic ceramide (ϩ7.4) 9) suggested that LMCer-1 has the same absolute configuration as that of the synthetic one for the core structure, the 2,3,2Ј part.…”

“…The 1 H-NMR signals of the basic structure of LMCer-1 were in good agreement with those of known synthetic ceramide 1b, 9) which is composed of (2S,3R,4E)-sphingosine and (R)-2-hydroxy fatty acid. The above fact and the optical rotation of the LMCer-1 series, LMCer-1-1 (ϩ3.3) (vide infra) and the synthetic ceramide (ϩ7.4) 9) suggested that LMCer-1 has the same absolute configuration as that of the synthetic one for the core structure, the 2,3,2Ј part. The component of LMCer-1 was examined.…”

Synthesis of (2S,2’R,3R,4E,8E)-N-2’-Hydroxyoctadecanoyl-1-O-(β-d-glucopyranosyl)-9-methyl-4,8-sphingadienine (Pen III), a Cerebroside Isolated fromPenicillium funiculosumas the Fruiting Inducer againstSchizophyllum commune

“…The separated acid was extracted with diethyl ether, and the ethereal solution was washed with brine, dried and concentrated in vacuo. The residue was recrystallized from petroleum ether to give 2.3 g (60%) of (± )-3 as needles, mp 56-57°C (± )-2-Hydroxyoctadecanoic acid (4). Sodium hydroxide (2.1 g, 50 mmol) in water (20 ml) was added to (± )-3 (2.3 g, 6.3 mmol), and the mixture was stirred and heated at 80"C for 24 h. After cooling, the mixture was acidified with hydrochloric acid, and extracted with diethyl ether.…”

“…The ethereal solution was sequentially washed with water and brine, dried with magnesium sulfate, and concentrated in vacuo. The (R)-2-Hydroxyoctadecanoic acid (4). Lipase PS (Amano Pharmaceutical Co.; 1.43 g) was suspended in a solution of ( ± )-4 (1.23 g, 4.1 mmol) and BHT (butylated hydroxy toluene, 12 mg) in vinyl acetate (14 ml) and tetrahydrofuran (14 ml), and the mixture was stirred at 65'C for 24 h. After cooling, the mixture was filtered through Celite, and the Celite layer was washed with diethyl ether.…”

“…1.2) The structure and (2S,2' R,3R,-4E,8E)-stereochemistry of Sch II were confirmed by its total synthesis in 1985 by Mori and Funaki. 3 ,4) In the same year of 1985, Kawai et al clarified the structures of the active substances produced by P. funiculosum as being four cerebrosides, Pen I-Pen IV, which were isolated in a ratio did not clearly mention the absolute configuration of Pen III, we assumed it to possess the same stereochemistry as that of Sch II. Sphingadienine B can then be dissected into two parts: aldehyde D and enyne E. Aldehyde D can be derived from L-serine (F) according to Garner et al,6) while enyne E has already been prepared by us from homoprenyl acetate (G).4) Hydroxy acid C can be prepared from stearic acid (H).…”