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【结 构 式】

【分子编号】42765

【品名】(2S,3S,4S)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-3-[(triethylsilyl)oxy]-1-pentanol

【CA登记号】

【 分 子 式 】C24H42O5Si

【 分 子 量 】438.67998

【元素组成】C 65.71% H 9.65% O 18.24% Si 6.4%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(XXXIII)

The intermediate (XLI) has been obtained as follows: The condensation of the silylated propionic aldehyde (I) with the chiral allene (XXIII) by means of BF3/Et2O gives the acetylenic alcohol (XXIV), which is desilylated with TBAF, yielding the diol (XXV). The reaction of (XXV) with p-methoxybenzaldehyde dimethyl acetal (XXVI) affords the cyclic ketal (XXVII), which is treated with Red-Al to provided the primary alcohol (XXVIII). The asymmetric Sharpless epoxidation of the double bond of (XXVIII) gives the epoxide (XXIX), which is methylated with Me2CuCNLi2, yielding the chiral diol (XXX). The regioselective acylation of (XXX) with pivaloyl chloride affords the monopivalate (XXXI), which is silylated with Tes-Otf, providing the silyl ether (XXXII). The reductive cleavage of the pivalate ester of (XXXII) with Red-Al furnishes the primary alcohol (XXXIII), which is oxidized with DMP to the aldehyde (XXXIV). The condensation of (XXXIV) with the bromoallyl compound (XXXV) gives the homoallyl alcohol (XXXVI), which is treated with NaH in THF to afford the conjugated diene (XXXVII) (2). The reductive cleavage of the cyclic ketal group of (XXXVII) with iBu2AlH gives the primary alcohol (XXXVIII), which is treated with I2 and PPh3 to yield the iodo derivative (XXXIX). Finally, this compound is condensed with 9-methoxy-9-borabicyclo[3,3,1]nonane (XL) by means of BuLi in THF/ethyl ether to furnish the desired intermediate, the lithium salt (XLI).

1 Marshall, J.A.; Hohns, B.A.; Total synthesis of (+)-discodermolide. J Org Chem 1998, 63, 22, 7885.
2 Marsshall, J.A.; et al.; Synthesis of discodermolide subunits by SE2' addition of nonracemic allenylstannanes to aldehydes. J Org Chem 1998, 63, 3, 817.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(I) 42735 (2S)-2-methyl-3-[(triethylsilyl)oxy]propanal C10H22O2Si 详情 详情
(XXIII) 42756 2-(tributylstannyl)-2,3-pentadienyl pivalate C22H42O2Sn 详情 详情
(XXIV) 42757 (4R,5S,6S)-5-hydroxy-4,6-dimethyl-7-[(triethylsilyl)oxy]-2-heptynyl pivalate C20H38O4Si 详情 详情
(XXV) 42758 (4R,5S,6S)-5,7-dihydroxy-4,6-dimethyl-2-heptynyl pivalate C14H24O4 详情 详情
(XXVI) 26485 1-(dimethoxymethyl)-4-methoxybenzene 2186-92-7 C10H14O3 详情 详情
(XXVII) 42759 (4R)-4-[(2R,4S,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-pentynyl pivalate C22H30O5 详情 详情
(XXVIII) 42760 (E,4R)-4-[(2R,4S,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-penten-1-ol C17H24O4 详情 详情
(XXIX) 42761 ((2S,3R)-3-[(1R)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]oxiranyl)methanol C17H24O5 详情 详情
(XXX) 42762 (2S,3S,4R)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-1,3-pentanediol C18H28O5 详情 详情
(XXXI) 42763 (2S,3S,4R)-3-hydroxy-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methylpentyl pivalate C23H36O6 详情 详情
(XXXII) 42764 (2S,3S,4S)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-3-[(triethylsilyl)oxy]pentyl pivalate C29H50O6Si 详情 详情
(XXXIII) 42765 (2S,3S,4S)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-3-[(triethylsilyl)oxy]-1-pentanol C24H42O5Si 详情 详情
(XXXIV) 42766 (2R,3R,4S)-4-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-2-methyl-3-[(triethylsilyl)oxy]pentanal C24H40O5Si 详情 详情
(XXXV) 42629 (1-bromo-2-propenyl)(trimethyl)silane 94397-40-7 C6H13BrSi 详情 详情
(XXXVI) 42767 (3S,4R,5S,6S,7S)-7-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]-5-methyl-6-[(triethylsilyl)oxy]-3-(trimethylsilyl)-1-octen-4-ol C30H54O5Si2 详情 详情
(XXXVII) 42768 triethyl[((1S,2S,3Z)-1-[(1S)-1-[(2R,4R,5S)-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]ethyl]-2-methyl-3,5-hexadienyl)oxy]silane; 4-((2R,4R,5S)-4-[(1S,2S,3S,4Z)-1,3-dimethyl-2-[(triethylsilyl)oxy]-4,6-heptadienyl]-5-methyl-1,3-dioxan-2-yl)phenyl methyl ether C27H44O4Si 详情 详情
(XXXVIII) 42769 (2S,3R,4S,5S,6S,7Z)-3-[(4-methoxybenzyl)oxy]-2,4,6-trimethyl-5-[(triethylsilyl)oxy]-7,9-decadien-1-ol C27H46O4Si 详情 详情
(XXXIX) 42770 triethyl[((1S,2S,3Z)-1-[(1S,2S,3R)-4-iodo-2-[(4-methoxybenzyl)oxy]-1,3-dimethylbutyl]-2-methyl-3,5-hexadienyl)oxy]silane; (1S,2S,3Z)-1-[(1S,2S,3R)-4-iodo-2-[(4-methoxybenzyl)oxy]-1,3-dimethylbutyl]-2-methyl-3,5-hexadienyl triethylsilyl ether C27H45IO3Si 详情 详情
(XL) 42771 9-methoxy-9-borabicyclo[3.3.1]nonane 38050-71-4 C9H17BO 详情 详情
(XLI) 42772   C36H62BLiO4Si 详情 详情
Extended Information