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【结 构 式】

【分子编号】36888

【品名】(2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-4-pentyn-2-ol

【CA登记号】

【 分 子 式 】C18H30O2Si

【 分 子 量 】306.5205

【元素组成】C 70.53% H 9.86% O 10.44% Si 9.16%

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:(XI)

The chiral 6(R) isomer of 213351 has been obtained as follows: The condensation of 1,1-diacetylcyclopropane monoethylene ketal (I) with acetylenic phosphonate (II) by means of NaHMDS in THF gives the silylated pentenyne (III), which is treated with TsOH in acetone/water yielding the acetylcyclopropane (IV). The Sharpless asymetric dihydroxylation of the double bond of (IV) by means of chiral auxiliary (DHQD)2PYR, K2OsO2(OH)4, K3Fe(CN)6 and K2CO3 in tert-butanol/water affords the chiral diol (V), which is monosilylated with TBDMS-OTf providing the silyl ether (VI). The condensation of (VI) with ethynylmagnesium bromide (VII) and CeCl3 gives the diacetylenic diol (VIII), which is regioselectively acetylated with Ac2O, TEA and DMAP yielding the monoacetate (IX). The treatment of the propargylic acetate (IX) with [(PPh3)CuH]6 in methanol affords the allene (X), which is regioselectively desilylated at the terminal acetylenic group furnishing the cyclization precursor (XI). The Mo(CO)6 promoted cyclization of (XI) in refluxing toluene/DMSO gives the chiral tricyclic ketone (XII). The methylation of (XII) with MeLi yields the monosilylated diol (XIII), which is desilylated with TBAF to the chiral diol (XIV). The oxidation of (XIV) with Dess Martin periodinane (DMP) affords the chiral hydroyketone (XV), which is finally hydroxymethylated with formaldehyde and H2SO4 to furnish the target compound.

1 Brummond, K.M.; et al.; A rapid synthesis of hydroxymethylacylfulvene (HMAF) using the allenic Pauson - Khand reaction. A synthetic approach to either enantiomer of this illudane structure. J Am Chem Soc 2000, 122, 20, 4915.
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) 36876 1-[1-(2-methyl-1,3-dioxolan-2-yl)cyclopropyl]-1-ethanone C9H14O3 详情 详情
(II) 36877 diethyl 3-(trimethylsilyl)-2-propynylphosphonate C10H21O3PSi 详情 详情
(III) 36878 trimethyl[(Z)-4-[1-(2-methyl-1,3-dioxolan-2-yl)cyclopropyl]-3-penten-1-ynyl]silane C15H24O2Si 详情 详情
(IV) 36879 1-[1-[(Z)-1-methyl-4-(trimethylsilyl)-1-buten-3-ynyl]cyclopropyl]-1-ethanone C13H20OSi 详情 详情
(V) 36880 1-[1-[(1R,2R)-1,2-dihydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-ethanone C13H22O3Si 详情 详情
(VI) 36881 1-[1-[(1R,2R)-2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-ethanone C19H36O3Si2 详情 详情
(VII) 17778 ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium 4301-14-8 C2HBrMg 详情 详情
(VIII) 36882 (2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-hydroxy-1-methyl-2-propynyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol C21H38O3Si2 详情 详情
(IX) 36883 1-[1-[(1R,2R)-2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-methyl-2-propynyl acetate C23H40O4Si2 详情 详情
(X) 36884 (2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol C21H38O2Si2 详情 详情
(XI) 36888 (2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-4-pentyn-2-ol C18H30O2Si 详情 详情
(XII) 36885   C19H30O3Si 详情 详情
(XIII) 36886   C20H32O2Si 详情 详情
(XIV) 36887   C14H18O2 详情 详情
(XV) 26689 6(R)-6-Hydroxy-2,4,6-trimethyl-6,7-dihydro-5H-spiro[indene-5,1'-cyclopropan]-7-one; 6(R)-6-Hydroxy-2,4,6-trimethyl-6,7-dihydro-5H-spiro[indene-5,1'-cyclopropan]-7-one C14H16O2 详情 详情
Extended Information