Synthetic studies of erythromycins. IV. Total synthesis of erythronolide A.
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概要
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The enantiospecific total synthesis of erythronolide A (<B>1</B>) through (9<I>S</I>)-9-deoxo-9-hydroxyerythronolide A (<B>2</B>) from the chiral C1–C6, C7–C9, and C10–C13 synthetic segments is described. The C10–C13 segment, (3<I>R</I>,4<I>R</I>,5<I>R</I>)-5-<I>O</I>-benzyl-2-iodo-3,4-<I>O</I>-isopropylidene-4-methyl-1-heptene-3,4,5-triol (<B>11</B>) was synthesized in 16 steps and an 8.3% overall yield from D-ribose. The C7–C9 segment, (<I>S</I>)-(+)-2-(2-bromo-1-methylethyl)-1,3-dioxolane (<B>47</B>) was prepared from methyl (<I>S</I>)-(+)-3-hydroxy-2-methylpropionate in 8 steps and a 49% overall yield. The coupling of the Grignard reagent, prepared from magnesium and <B>47</B>, and the C1–C6 segment, 3,5,7-tri-<I>O</I>-benzyl-1,4,6-trideoxy-4,6-di-<I>C</I>-methyl-<I>keto</I>-L-<I>ido</I>-2-heptulose (<B>13</B>), afforded 5,7,9-tri-<I>O</I>-benzyl-2,3,6,8-tetradeoxy-2,4,6,8-tetra-<I>C</I>-methyl-L-<I>threo</I>-L-<I>ido</I>-nonose ethylene acetal (<B>48</B>) and its C4-epimer in 79% and 8% yields, respectively. 5,7,9-Tri-<I>O</I>-benzyl-4-<I>O</I>-<I>t</I>-butyldimethylsilyl-2,3,6,8-tetradeoxy-2,4,6,8-tetra-<I>C</I>-methyl-L-<I>threo</I>-L-<I>ido</I>-nonose (<B>12</B>), derived from <B>48</B>, was subjected to coupling reaction with the lithium reagent prepared from <B>11</B> to afford about 5:1 excess of the "Cram" product <B>50</B>. The homogeneous hydrogenation of <B>50</B> with [ClRh(Ph<SUB>3</SUB>P)<SUB>3</SUB>] gave 1,3,5,13-tetra-<I>O</I>-benzyl-6-<I>O</I>-<I>t</I>-butyldimethylsilyl-2,4,7,8,10,14,15-heptadeoxy-11,12-<I>O</I>-isopropylidene-2,4,6,8,10,12-hexa-<I>C</I>-methyl-D-<I>arabino</I>-D-<I>gluco</I>-L-<I>ido</I>-pentadecitol (<B>54</B>) and its C10-epimer in 41% and 7% yields from <B>12</B>, respectively. The conversion of <B>54</B> to <B>2</B> was accomplished by a sequence of reactions including the Corey–Nicolaou lactonization method in a 17% overall yield. Selective 3,5-<I>O</I>-benzylidenation of <B>2</B> followed by PCC oxidation and debenzylidenation gave <B>1</B> in 52% yield.
- 公益社団法人 日本化学会の論文
著者
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Nakata Masaya
Department Of Applied Chemistry Faculty Of Science And Technology Keio University
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Tomooka Katsuhiko
Department Of Applied Chemistry Tokyo Institute Of Technology
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Arai Masayuki
Department Of Chemistry Tokyo Institute Of Technology
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Kinoshita Mitsuhiro
Department of Applied Chemistry Engineering Faculty of Keio University
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Tomooka Katsuhiko
Department of Applied Chemistry, Faculty of Science and Technology, Keio University
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Ohsawa Naoki
Department of Applied Chemistry, Faculty of Science and Technology, Keio University
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