(E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-hydroxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenoic acid -Drug Synthesis Database

【结构式】

【分子编号】61722

【品名】(E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-hydroxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenoic acid

【CA登记号】

【分子式】C₂₆H₃₈O₆Si

【分子量】474.66962

【元素组成】C 65.79% H 8.07% O 20.22% Si 5.92%

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：(XXIII)

The demethylation of (XXI) by means of BBr3 gives the hydroxyaldehyde (XXII), which is oxidized to the corresponding carboxylic acid (XXIII) by means of NaClO2. The protection of the phenolic OH group of (XXIII) by means of Tbdms-OTf and TEA yields the silyl ether (XXIV), which is submitted to a Curtius rearrangement by means of isobutyl chloroformate, NaN3 and 2-(trimethylsilyl)ethanol, affording the carbamate (XXV). The acylation of carbamate (XXV) with heptadienoyl chloride (XXVI) and NaHMDS provides the advanced intermediate (XXVII), which is finally deprotected by successive treatments with TBAF and with HF/pyridine to provide the target Salicylhalamide A.

参考文献中间体

合成目标

【1】 Smith, A.B.; Zheng, J.Y.; Total synthesis of (-)-salicylihalamide A and related congeners. Tetrahedron 2002, 58, 33, 6455.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XIV)	56950	(E)-4-((3S,5R,6S)-5,14-bis{[tert-butyl(dimethyl)silyl]oxy}-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenoic acid	C₃₂H₅₂O₆Si₂	详情	详情
(XXI)	61720	(E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-methoxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenal	C₂₇H₄₀O₅Si	详情	详情
(XXII)	61721	(E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-hydroxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenal	C₂₆H₃₈O₅Si	详情	详情
(XXIII)	61722	(E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-hydroxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenoic acid	C₂₆H₃₈O₆Si	详情	详情
(XXV)	61723	2-(trimethylsilyl)ethyl (E)-3-((3S,5R,6S)-5,14-bis{[tert-butyl(dimethyl)silyl]oxy}-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-1-propenylcarbamate	C₃₇H₆₅NO₆Si₃	详情	详情
(XXVI)	61725	(2Z,4Z)-2,4-heptadienoyl chloride	C₇H₉ClO	详情	详情
(XXVII)	61724	2-(trimethylsilyl)ethyl (E)-3-((3S,5R,6S)-5,14-bis{[tert-butyl(dimethyl)silyl]oxy}-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-1-propenyl[(2Z,4Z)-2,4-heptadienoyl]carbamate	C₄₄H₇₃NO₇Si₃	详情	详情

Extended Information