6-heptenal -Drug Synthesis Database

【结构式】

【分子编号】27179

【品名】6-heptenal

【CA登记号】

【分子式】C₇H₁₂O

【分子量】112.17168

【元素组成】C 74.95% H 10.78% O 14.26%

与该中间体有关的原料药合成路线共 2 条

合成路线1 合成路线2

合成路线1

该中间体在本合成路线中的序号：(III)

C7-C12 fragment.- The selective monoepoxidation of 1,7-octadiene (I) with m-chloroperbenzoic acid (MCPBA) gives the epoxide (II), which is oxidized with periodic acid to the aldehyde (III). Further oxidation of (III) by means of NaClO2 yields 6-heptenoic acid (IV), which is condensed with the lithium salt of the chiral oxazolidinone (V) by means of pivaloyl chloride affording the chiral imide (VI). The methylation of (VI) with methyl iodide and sodium hexamethyldisylazide (NaHMDS) in THF provides the methylated chiral imide (VII) as a single enantiomer. The hydrolysis of (VII) with H2O2 and LiOH gives the corresponding free acid (VIII), which is reduced with LiAlH4 to the primery alcohol (IX). Finally, (IX) is treated with Swern oxidant to afford the desired taret aldehyde (X).

参考文献中间体

合成目标

【1】 Taylor, R.E.; et al.; A formal total synthesis of epothiolone A: Enantioselective preparation of the C1-C6 and C7-C12 fragments. J Org Chem 1998, 63, 25, 9580.

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)	27177	1,7-octadiene	3710-30-3	C₈H₁₄	详情	详情
(II)	27178	2-(5-hexenyl)oxirane	19600-63-6	C₈H₁₄O	详情	详情
(III)	27179	6-heptenal		C₇H₁₂O	详情	详情
(IV)	27180	6-heptenoic acid	1119-60-4	C₇H₁₂O₂	详情	详情
(V)	10793	[(4S)-4-Benzyl-2-oxo-1,3-oxazolidin-3-yl]lithium		C₁₀H₁₀LiNO₂	详情	详情
(VI)	27181	(4S)-4-benzyl-3-(6-heptenoyl)-1,3-oxazolidin-2-one		C₁₇H₂₁NO₃	详情	详情
(VII)	27182	(4S)-4-benzyl-3-[(2S)-2-methyl-6-heptenoyl]-1,3-oxazolidin-2-one		C₁₈H₂₃NO₃	详情	详情
(VIII)	27183	(2S)-2-methyl-6-heptenoic acid		C₈H₁₄O₂	详情	详情
(IX)	27184	(2S)-2-methyl-6-hepten-1-ol		C₈H₁₆O	详情	详情
(X)	27185	(2S)-2-methyl-6-heptenal		C₈H₁₄O	详情	详情

合成路线2

该中间体在本合成路线中的序号：(II)

The aminoacid building block (VIII) can be prepared by two different ways. The oxidative cleavage of 7-octene-1,2-diol (I) by means of NaIO4 yields aldehyde (II). Partial hydrolysis of diethyl 2-acetamidomalonate (III) provides monoacid (IV), which is subjected to Knoevenagel-type condensation with 6-heptenal (II) in the presence of Ac2O and pyridine to afford enamide (V). Enantioselective hydrogenation of the enamide double bond to the (S)-amidoester (VI) is then achieved by using the Burk's method. In order to replace the N-acetyl protecting group of (VI), the acetamide nitrogen is protected with Boc2O, and the resulting imide (VII) is further hydrolyzed to the target N-Boc aminoacid (VIII) under standard basic conditions.

参考文献中间体

合成目标

【1】 Halmos, T.; Llinas-Brunet, M.; Faucher, A.-M.; Ghiro, E.; Goudreau, N.; Tsantrizos, Y.S.; Cameron, D.R. (Boehringer Ingelheim (Canada) Ltd.); Macrocyclic peptides active against the hepatitis C virus. EP 1169339; JP 2002542160; WO 0059929 .

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)	58933	7-Octene-1,2-diol		C₈H₁₆O₂	详情	详情
(II)	27179	6-heptenal		C₇H₁₂O	详情	详情
(III)	16170	1,2-dichloroethane	107-06-2	C₂H₄Cl₂	详情	详情
(IV)	58934	Ethyl 2-acetamidomalonate		C₇H₁₁NO₅	详情	详情
(V)	58935	ethyl (2Z)-2-(acetylamino)-2,8-nonadienoate		C₁₃H₂₁NO₃	详情	详情
(VI)	58936	ethyl (2S)-2-(acetylamino)-8-nonenoate		C₁₃H₂₃NO₃	详情	详情
(VII)	58937	(2S)-2-[acetyl(tert-butoxycarbonyl)amino]-8-nonenoic acid		C₁₆H₂₇NO₅	详情	详情
(VIII)	58938	(2S)-2-[(tert-butoxycarbonyl)amino]-8-nonenoic acid		C₁₄H₂₅NO₄	详情	详情

Extended Information