　 -Drug Synthesis Database

【结构式】

【分子编号】48957

【品名】　

【CA登记号】

【分子式】C₅₄H₉₉CuNO₄

【分子量】889.9304

【元素组成】C 72.88% H 11.21% Cu 7.14% N 1.57% O 7.19%

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：(XXV)

Synthesis of the intermediate vinyl cuprate (XXV): The reaction of cyclohexyloxyacetylene (XXI) with iso-butyl triflate (XXII) by means of BuLi gives the adduct (XXIII), which is brominated with Tms-Br, yielding the vinyl bromide (XXIV). Finally, this compound is treated with CuCN, LiCl and tBuLi in THF to afford the desired vinyl cuprate intermediate (XXV).

参考文献中间体

合成目标

【1】 Jin, Z.; Yu, W.; A new strategy for the stereoselective introduction of steroid side chain via alpha-alkoxy vinyl cuprates: Total synthesis of a highly potent antitumor natural product OSW-1. J Am Chem Soc 2001, 123, 14, 3369.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XXI)	48953	1-(ethynyloxy)cyclohexane; cyclohexyl ethynyl ether	C₈H₁₂O	详情	详情
(XXII)	48954	isobutyl trifluoromethanesulfonate	C₅H₉F₃O₃S	详情	详情
(XXIII)	48955	1-[(4-methyl-1-pentynyl)oxy]cyclohexane; cyclohexyl 4-methyl-1-pentynyl ether	C₁₂H₂₀O	详情	详情
(XXIV)	48956	(E)-1-bromo-4-methyl-1-pentenyl cyclohexyl ether; 1-[[(E)-1-bromo-4-methyl-1-pentenyl]oxy]cyclohexane	C₁₂H₂₁BrO	详情	详情
(XXV)	48957		C₅₄H₉₉CuNO₄	详情	详情

合成路线2

该中间体在本合成路线中的序号：(XXV)

Synthesis of the cholestane aglycon (XXXVI): The protection of the OH group of dehydroisoandrosterone (XXVI) with Tbdms-Cl and imidazole gives the silyl ether (XXVII), which is condensed with ethyl triphenylphosphonium bromide (XXVIII) and potassium tert-butoxide in refluxing THF to yield the ethylidene compound (XXIX). The hydroxylation of (XXIX) with SeO2 and TBHP affords the 16alpha-hydroxy compound (XXX), which by a Swern oxidation is converted into the ketone (XXXI). The condensation of (XXXI) with the intermediate cuprate (XXV) provides the adduct (XXXII), which is treated with ethyleneglycol (XXXIII) and PPTS to give the spiroketal (XXXIV). The oxidative cleavage of the enol acetate of (XXXIV) with tBu-OK and Davis reagent yields the alpha-hydroxyketone (XXXV), which is finally reduced with LiAlH4 to afford the desired cholestane aglycon (XXXVI).

参考文献中间体

合成目标

【1】 Jin, Z.; Yu, W.; A new strategy for the stereoselective introduction of steroid side chain via alpha-alkoxy vinyl cuprates: Total synthesis of a highly potent antitumor natural product OSW-1. J Am Chem Soc 2001, 123, 14, 3369.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(XXV)	48957			C₅₄H₉₉CuNO₄	详情	详情
(XXVI)	11713	Dehydroepiandrosterone;prasterone；(3S,8R,9S,10R,13S,14S)-3-Hydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one	53-43-0	C₁₉H₂₈O₂	详情	详情
(XXVII)	16818	(3S,8R,9S,10R,13S,14S)-3-[[tert-butyl(dimethyl)silyl]oxy]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one		C₂₅H₄₂O₂Si	详情	详情
(XXVIII)	11717	Ethyl(triphenyl)phosphonium bromide; (Ethyl)triphenylphosphonium bromide	1530-32-1	C₂₀H₂₀BrP	详情	详情
(XXIX)	48958	tert-butyl(dimethyl)silyl (3S,10R,13S)-17-[(Z)ethylidene]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-3-yl ether; tert-butyl([(3S,10R,13S)-17-[(Z)ethylidene]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-3-yl]oxy)dimethylsilane		C₂₇H₄₆OSi	详情	详情
(XXX)	48959	(3S,10R,13S,16R)-3-[[tert-butyl(dimethyl)silyl]oxy]-17-[(E)ethylidene]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-16-ol		C₂₇H₄₆O₂Si	详情	详情
(XXXI)	48960	(3S,10R,13S)-3-[[tert-butyl(dimethyl)silyl]oxy]-17-[(E)ethylidene]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,17-tetradecahydro-16H-cyclopenta[a]phenanthren-16-one		C₂₇H₄₄O₂Si	详情	详情
(XXXII)	48961	(3S,10R,13S)-3-[[tert-butyl(dimethyl)silyl]oxy]-17-[(1S,2Z)-2-(cyclohexyloxy)-1,5-dimethyl-2-hexenyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-16-yl acetate		C₄₁H₆₈O₄Si	详情	详情
(XXXIII)	11295	Polyethylene glycol;1,2-Ethanediol;Monoethylene glycol; Ethylene glycol	107-21-1	C₂H₆O₂	详情	详情
(XXXIV)	48962	(3S,10R,13S)-3-[[tert-butyl(dimethyl)silyl]oxy]-17-[(1S)-1-(2-isopentyl-1,3-dioxolan-2-yl)ethyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-16-yl acetate		C₃₇H₆₂O₅Si	详情	详情
(XXXV)	48963	(3S,10R,13S,17S)-3-[[tert-butyl(dimethyl)silyl]oxy]-17-hydroxy-17-[(1S)-1-(2-isopentyl-1,3-dioxolan-2-yl)ethyl]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,17-tetradecahydro-16H-cyclopenta[a]phenanthren-16-one		C₃₅H₆₀O₅Si	详情	详情
(XXXVI)	48964	(3S,10R,13S,16S,17S)-3-[[tert-butyl(dimethyl)silyl]oxy]-17-[(1S)-1-(2-isopentyl-1,3-dioxolan-2-yl)ethyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-16,17-diol		C₃₅H₆₂O₅Si	详情	详情

Extended Information