(3S,4R)-3,4-dihydroxy-1-cyclohexene-1-carbaldehyde -Drug Synthesis Database

【结构式】

【分子编号】52851

【品名】(3S,4R)-3,4-dihydroxy-1-cyclohexene-1-carbaldehyde

【CA登记号】

【分子式】C₇H₁₀O₃

【分子量】142.1546

【元素组成】C 59.14% H 7.09% O 33.76%

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：(XXV)

The synthesis of the racemic fumagillol (+/-)-(XXII) has also been reported. Regioselective dihydroxylation of 1,3-cyclohexadiene-1-carbaldehyde (XXIV) using N-methylmorpholine-N-oxide in the presence of a catalytic amount of OsO4 afforded the cis-diol (XXV), which was further protected as the isopropylidene ketal (XXVI). Conjugate addition to (XXVI) of the organocuprate reagent derived from vinyl bromide (XXVII) in the presence of BF3·Et2O produced (XXVIII) as a mixture of epimers at C-1, which were used without separation. Aldehyde (XXVIII) was converted to the cyclohexyl nitrone (XXX) upon treatment with N-cyclohexyl hydroxylamine (XXIX) and NaHCO-3. Acetylation of (XXX) produced a transitory N-vinyl-O-acetylhydroxylamine (XXXI) which underwent a [3,3] sigmatropic rearrangement to the alpha-acetoxy-N-cyclohexylimine (XXXII). Selective hydrolysis of the imine function of (XXXII) using HOAc/NaOAc furnished aldehyde (XXXIII). This was reduced with LiAlH4, followed by acidic hydrolysis of the isopropylidene ketal to yield the tetraol (XXXIV).

参考文献中间体

合成目标

【1】 Vosburg, D.A.; et al.; A concise synthesis of fumagillol. Angew Chem. Int Ed 1999, 38, 7, 971.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XXVIIIIa)	52854	(3aS,4S,5R,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxole-5-carbaldehyde	C₁₈H₂₈O₃	详情	详情
(XXVIIIIb)	52855	(3aS,4S,5S,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxole-5-carbaldehyde	C₁₈H₂₈O₃	详情	详情
(XXIV)	52850	1,3-cyclohexadiene-1-carbaldehyde	C₇H₈O	详情	详情
(XXV)	52851	(3S,4R)-3,4-dihydroxy-1-cyclohexene-1-carbaldehyde	C₇H₁₀O₃	详情	详情
(XXVI)	52852	(3aS,7aR)-2,2-dimethyl-3a,6,7,7a-tetrahydro-1,3-benzodioxole-5-carbaldehyde	C₁₀H₁₄O₃	详情	详情
(XXVII)	52853	(2E)-2-bromo-6-methyl-2,5-heptadiene	C₈H₁₃Br	详情	详情
(XXIX)	52856	N-Cyclohexylhydroxylamine	C₆H₁₃NO	详情	详情
(XXX)	52857	((Z)-{(3aS,4S,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxol-5-yl}methylidene)(cyclohexyl)ammoniumolate	C₂₄H₃₉NO₃	详情	详情
(XXXI)	52858	(3aS,4R,7aR)-5-{(E)-[(acetyloxy)(cyclohexyl)amino]methylidene}-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxole	C₂₆H₄₁NO₄	详情	详情
(XXXII)	52859	(3aS,4S,5R,7aR)-5-[(cyclohexylimino)methyl]-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-2,2-dimethylhexahydro-1,3-benzodioxol-5-yl acetate	C₂₆H₄₁NO₄	详情	详情
(XXXIII)	52860	(3aS,4S,5R,7aR)-4-[(1E)-1,5-dimethyl-1,4-hexadienyl]-5-formyl-2,2-dimethylhexahydro-1,3-benzodioxol-5-yl acetate	C₂₀H₃₀O₅	详情	详情
(XXXIV)	52861	(1R,2S,3S,4R)-3-[(1E)-1,5-dimethyl-1,4-hexadienyl]-4-(hydroxymethyl)-1,2,4-cyclohexanetriol	C₁₅H₂₆O₄	详情	详情

Extended Information