Synthesis of (4,8,2,3,2')--2' -hydroxyhexadecanoyl-9-methyl-4,8-sphingadiemine, the ceramide portion of the fruiting-inducing cerebroside in a basidiomycete , and its (2,3)-isomer

Ceramide Constituents from Five Mushrooms.

“…octadecadiene-1,3-diol (4) and (2S,2ЈR,3R,4E,8E)-N-2Ј-hydroxytetradecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (5), as well as (2S,2ЈR,3R,4E,8E)-N-2Ј-hydroxyhexadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (3), a known synthetic compound, 6) from five mushrooms, Panellus serotinus (PERS. : FR.)…”

“…Compound 3 was isolated from a natural source for the first time, although 3 has already been synthesized by Mori and Funaki. 6) Compound 4 was isolated as an amorphous powder. The molecular formula was determined to be C 34 H 65 NO 4 by HR-EI-MS.…”

“…The Et 2 O extract (3.7 g) was chromatographed on a silica gel column using hexane-EtOAc (7 : 3-1 : 7), EtOAc and MeOH, to afford 20 fractions (frs. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Fraction 17 was purified by preparative HPLC to give 3 (1.9 mg) and 4 (1.8 mg).…”

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

“…Oxazolidinecarbaldehyde 7 was treated with an acetyl ide generated from 8 3 ) to give 9 in an 85% yield after chromatographic purification. Reduction of 9 with lithium in ethylamine was followed by acid treatment of the product to effect the formation of the E-double bond at C-4 and also deprotection to give crude (2S,3R,4E,8E)-9-methyl-4,8-sphingadienine (10 = B).…”

Synthesis and Biological Activity of the Isomers and Analogs of (4E,8E,2S,3R,2′R)-N-2′-Hydroxyhexadecanoyl-9-methyl-4,8-sphingadienine, the Ceramide Portion of the Fruiting-inducing Cerebroside in a BasidiomyceteSchizophyllum commune

“…6 ) The (Z)-alcohol 9a 5 ) was converted to a bromide 10 in the conventional manner via a tosylate 9b. The bromide 10 was converted to a nitrile 11, whose reduction with DIBAL-H furnished an aldehyde 12.…”