　 -Drug Synthesis Database

【结构式】

【分子编号】35697

【品名】　

【CA登记号】

【分子式】C₅₀H₇₈O₆S₂Si

【分子量】867.38322

【元素组成】C 69.24% H 9.06% O 11.07% S 7.39% Si 3.24%

与该中间体有关的原料药合成路线共 4 条

合成路线1 合成路线2 合成路线3 合成路线4

合成路线1

该中间体在本合成路线中的序号：(XXV)

The cyclization of (XVII) by means of Me2AlCl in dichloromethane gives the tricyclic ketone (XVIII), which is desilylated with TBAF in THF yielding the ethanol (XIX). The oxidation of (XIX) with Dess Martin periodinane (DMP) in dichloromethane affords the corresponding aldehyde (XX), which is condensed with the lithium 1,3-dithiane (XXI) in THF to give the secondary alcohol (XXII). The silylation of this alcohol with Tes-OTf and NaH in THF yields the silyl ether (XXIII), which is treated with Ph-NTf2 and KHMDS in THF to afford the enol ether (XXIV). The reaction of (XXIV) with Pdo and CO in methanol gives the methyl ester (XXV), which is treated with PhI(OCOCF3)2 and methanol to afford the gem-dimethoxy compound (XXVI).

参考文献中间体

合成目标

【1】 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-263,114 and CP-225,917 - Part 1: Synthesis of key intermediates and intelligence gathering. Angew Chem. Int Ed Engl 1999, 38, 11, 1669.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XVII)	35689	(E)-1-(5-[(2E,9E)-1-[(E)-2-(4-methoxyphenyl)ethylidene]-2,9-undecadienyl]-2,2-dimethyl-1,3-dioxan-5-yl)-7-[(triisopropylsilyl)oxy]-4-hepten-3-one	C₄₂H₆₈O₅Si	详情	详情
(XVIII)	35690		C₄₂H₆₈O₅Si	详情	详情
(XIX)	35691		C₃₃H₄₈O₅	详情	详情
(XX)	35692		C₃₃H₄₆O₅	详情	详情
(XXI)	35693	[2-[(E)-3-pentenyl]-1,3-dithian-2-yl]lithium	C₉H₁₅LiS₂	详情	详情
(XXII)	35694		C₄₂H₆₂O₅S₂	详情	详情
(XXIII)	35695		C₄₈H₇₆O₅S₂Si	详情	详情
(XXIV)	35696		C₄₉H₇₅F₃O₇S₃Si	详情	详情
(XXV)	35697		C₅₀H₇₈O₆S₂Si	详情	详情
(XXVI)	35698		C₄₉H₇₈O₈Si	详情	详情

合成路线2

该中间体在本合成路线中的序号：(XXIX)

The reaction of (XXVIII) with Pd and CO in MeOH gives the methyl ester (XXIX), which is treated with PhI(OCOCF3)2 and MeOH to afford the gem-dimethoxy compound (XXX). The reduction of the ester group of (XXX) with DIBAL in toluene gives the carbinol (XXXI), which is treated with tert-butyl hydroperoxide and Et2Al-CN in toluene to yield the dihydroxycarbonitrile (XXXII). The sulfonation of the primary OH group of (XXXII) with MsCl affords the mesylate (XXXIII), which is treated with K2CO3 in MeOH providing the intermediate epoxide (XXXIV). The reaction of (XXXIV) with oxalic acid in EtOH/H2O affords the maleic anhydride derivative (XXXV).

参考文献中间体

合成目标

【1】 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-263,114 and CP-225,917 - Part 1: Synthesis of key intermediates and intelligence gathering. Angew Chem. Int Ed Engl 1999, 38, 11, 1669.
【2】 Nicolaou, K.C.; et al.; The absolute configuration and asymmetric total synthesis of the CP molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). Angew Chem. Int Ed Engl 2000, 39, 10, 1829.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
	15713	Oxalic acid	144-62-7	C₂H₂O₄	详情	详情
(XXVIII)	35696			C₄₉H₇₅F₃O₇S₃Si	详情	详情
(XXIX)	35697			C₅₀H₇₈O₆S₂Si	详情	详情
(XXX)	35698			C₄₉H₇₈O₈Si	详情	详情
(XXXI)	35699			C₄₈H₇₈O₇Si	详情	详情
(XXXII)	35700			C₄₉H₇₉NO₈Si	详情	详情
(XXXIII)	40299			C₅₁H₈₃NO₈SSi	详情	详情
(XXXIV)	35702			C₄₉H₇₇NO₇Si	详情	详情
(XXXV)	35703			C₄₉H₇₄O₉Si	详情	详情

合成路线3

该中间体在本合成路线中的序号：(XXV)

参考文献中间体

合成目标

【1】 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-263,114 and CP-225,917 - Part 1: Synthesis of key intermediates and intelligence gathering. Angew Chem. Int Ed Engl 1999, 38, 11, 1669.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XVII)	35689	(E)-1-(5-[(2E,9E)-1-[(E)-2-(4-methoxyphenyl)ethylidene]-2,9-undecadienyl]-2,2-dimethyl-1,3-dioxan-5-yl)-7-[(triisopropylsilyl)oxy]-4-hepten-3-one	C₄₂H₆₈O₅Si	详情	详情
(XVIII)	35690		C₄₂H₆₈O₅Si	详情	详情
(XIX)	35691		C₃₃H₄₈O₅	详情	详情
(XX)	35692		C₃₃H₄₆O₅	详情	详情
(XXI)	35693	[2-[(E)-3-pentenyl]-1,3-dithian-2-yl]lithium	C₉H₁₅LiS₂	详情	详情
(XXII)	35694		C₄₂H₆₂O₅S₂	详情	详情
(XXIII)	35695		C₄₈H₇₆O₅S₂Si	详情	详情
(XXIV)	35696		C₄₉H₇₅F₃O₇S₃Si	详情	详情
(XXV)	35697		C₅₀H₇₈O₆S₂Si	详情	详情
(XXVI)	35698		C₄₉H₇₈O₈Si	详情	详情

合成路线4

该中间体在本合成路线中的序号：(XXIX)

The reaction of (XXVIII) with Pd and CO in MeOH gives the methyl ester (XXIX), which is treated with PhI(OCOCF3)2 and MeOH to afford the gem-dimethoxy compound (XXX). The reduction of the ester group of (XXX) with DIBAL in toluene gives the carbinol (XXXI), which is treated with tert-butyl hydroperoxide and Et2Al(CN) in toluene to yield the dihydroxycarbonitrile (XXXII). The sulfonation of the primary OH group of (XXXII) with MsCl affords mesylate (XXXIII), which is treated with K2CO3 in MeOH providing intermediate epoxide (XXXIV). The reaction of (XXXIV) with oxalic acid affords the maleic anhydride derivative (XXXV).

参考文献中间体

合成目标

【1】 Nicolaou, K.C.; et al.; The absolute configuration and asymmetric total synthesis of the CP molecules (CP-263,114 and CP-225,917, Phomoidrides B and A). Angew Chem. Int Ed Engl 2000, 39, 10, 1829.
【2】 Nicolaou, K.C.; et al.; Total synthesis of the CP molecules CP-263,114 and CP-225,917 - Part 1: Synthesis of key intermediates and intelligence gathering. Angew Chem. Int Ed Engl 1999, 38, 11, 1669.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
	15713	Oxalic acid	144-62-7	C₂H₂O₄	详情	详情
(XXVIII)	35696			C₄₉H₇₅F₃O₇S₃Si	详情	详情
(XXIX)	35697			C₅₀H₇₈O₆S₂Si	详情	详情
(XXX)	35698			C₄₉H₇₈O₈Si	详情	详情
(XXXI)	35699			C₄₈H₇₈O₇Si	详情	详情
(XXXII)	35700			C₄₉H₇₉NO₈Si	详情	详情
(XXXIII)	40299			C₅₁H₈₃NO₈SSi	详情	详情
(XXXIV)	35702			C₄₉H₇₇NO₇Si	详情	详情
(XXXV)	35703			C₄₉H₇₄O₉Si	详情	详情

Extended Information