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【结 构 式】

【分子编号】60123

【品名】(2E,4E,7S,8E)-7-{[tert-butyl(dimethyl)silyl]oxy}-9-iodo-8-methyl-2,4,8-nonatrienal

【CA登记号】

【 分 子 式 】C16H27IO2Si

【 分 子 量 】406.37915

【元素组成】C 47.29% H 6.7% I 31.23% O 7.87% Si 6.91%

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:(XXVIII)

Chiral tetracyclic macrolactone (XXXVI): The condensation of the chiral aldehyde (XXV) with phosphonate (XXVI) in the usual way gives the nonatrienoic ester (XXVII), which is reduced with DIBAL to the corresponding alcohol and oxidized with MnO2 to the carbaldehyde (XXVIII). The condensation of (XXVIII) with the chiral oxazolidinone intermediate (VI) through its boron enolate yields the expected adduct (XXIX), which is reduced with Me4NBH(OAc)3 to afford the dihydroxy compound (XXX). The dethioacetalization of (XXX) by means of PhI(OCOCF3)2 in dichloromethane provides the cyclic ketal (XXXI). The regiocontrolled reduction of (XXXI) by means of NaBH4 in THF/water cleaves the chiral auxiliary to yield the carbinol (XXXII), which is successively oxidized with DMP and NaClO2 to afford the carboxylic acid (XXXIII) (1). The condensation of (XXXIII) with the chiral tripeptide intermediate (XV) by means of TBAF, HATU and DIEA in acetonitrile provides the corresponding amide (XXXIV), which is submitted to macrocyclization by means of LiOH, EDC and DIEA in dichloromethane to give the polycyclic macrolactone (XXXV). Finally, the Boc protecting group of (XXXV) is removed by means of Tms-OTf and lutidine in dichloromethane to afford the target chiral tetracyclic macrolactone (XXXVI)

1 Duan, M.S.; Paquette, L.A.; Enantioselective total synthesis of the cyclophilin-binding immunosuppressive agent sanglifehrin A. Angew Chem. Int Ed 2001, 40, 19, 3632.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(VI) 60104 (2R)-1-[(4S)-4-benzyl-2-oxo-1,3-oxazolidin-3-yl]-2-[2-(2-methyl-1,3-dithian-2-yl)ethyl]-1,3-pentanedione C22H29NO4S2 详情 详情
(XV) 60112 methyl (3S)-1-((2S)-2-{[(2S)-2-amino-3-methylbutanoyl]amino}-3-{3-[(tert-butoxycarbonyl)oxy]phenyl}propanoyl)hexahydro-3-pyridazinecarboxylate C25H38N4O7 详情 详情
(XXV) 32438 (3S,4E)-3-[[tert-butyl(dimethyl)silyl]oxy]-5-iodo-4-methyl-4-pentenal C12H23IO2Si 详情 详情
(XXVI) 60121 methyl (E)-4-(dipropoxyphosphoryl)-2-butenoate C11H21O5P 详情 详情
(XXVII) 60122 methyl (2E,4E,7S,8E)-7-{[tert-butyl(dimethyl)silyl]oxy}-9-iodo-8-methyl-2,4,8-nonatrienoate C17H29IO3Si 详情 详情
(XXVIII) 60123 (2E,4E,7S,8E)-7-{[tert-butyl(dimethyl)silyl]oxy}-9-iodo-8-methyl-2,4,8-nonatrienal C16H27IO2Si 详情 详情
(XXIX) 60124 (2R,4S,5S,6E,8E,11S,12E)-1-[(4S)-4-benzyl-2-oxo-1,3-oxazolidin-3-yl]-11-{[tert-butyl(dimethyl)silyl]oxy}-5-hydroxy-13-iodo-4,12-dimethyl-2-[2-(2-methyl-1,3-dithian-2-yl)ethyl]-6,8,12-tridecatriene-1,3-dione C38H56INO6S2Si 详情 详情
(XXX) 60125 (4S)-4-benzyl-3-{(2R,3R,4S,5S,6E,8E,11S,12E)-11-{[tert-butyl(dimethyl)silyl]oxy}-3,5-dihydroxy-13-iodo-4,12-dimethyl-2-[2-(2-methyl-1,3-dithian-2-yl)ethyl]-6,8,12-tridecatrienoyl}-1,3-oxazolidin-2-one C38H58INO6S2Si 详情 详情
(XXXI) 60126 (4S)-4-benzyl-3-{[(3S,4R,5R,6R)-3-((1E,3E,6S,7E)-6-{[tert-butyl(dimethyl)silyl]oxy}-8-iodo-7-methyl-1,3,7-octatrienyl)-1,4-dimethyl-2,9-dioxabicyclo[3.3.1]non-6-yl]carbonyl}-1,3-oxazolidin-2-one C35H50INO6Si 详情 详情
(XXXII) 60127 [(3S,4R,5S,6S)-3-((1E,3E,6S,7E)-6-{[tert-butyl(dimethyl)silyl]oxy}-8-iodo-7-methyl-1,3,7-octatrienyl)-1,4-dimethyl-2,9-dioxabicyclo[3.3.1]non-6-yl]methanol C25H43IO4Si 详情 详情
(XXXIII) 60128 (3S,4R,5R,6R)-3-((1E,3E,6S,7E)-6-{[tert-butyl(dimethyl)silyl]oxy}-8-iodo-7-methyl-1,3,7-octatrienyl)-1,4-dimethyl-2,9-dioxabicyclo[3.3.1]nonane-6-carboxylic acid C25H41IO5Si 详情 详情
(XXXIV) 60129 methyl (3S)-1-[(2S)-3-{3-[(tert-butoxycarbonyl)oxy]-1,3-cyclohexadien-1-yl}-2-({(2S)-2-[({(3S,4R,5R,6R)-3-[(1E,3E,6S,7E)-6-hydroxy-8-iodo-7-methyl-1,3,7-octatrienyl]-1,4-dimethyl-2,9-dioxabicyclo[3.3.1]non-6-yl}carbonyl)amino]-3-methylbutanoyl}amino)propanoyl]hexahydro-3-pyridazinecarboxylate C44H65IN4O11 详情 详情
(XXXV) 60130 tert-butyl 3-({(4R,7S,10S,16S,19S,25S,26R,27R)-19-[(E)-2-iodo-1-methylethenyl]-7-isopropyl-1,26-dimethyl-5,8,11,17-tetraoxo-18,28,29-trioxa-6,9,12,30-tetraazatetracyclo[23.3.1.1~12,16~.0~4,27~]triaconta-21,23-dien-10-yl}methyl)phenyl carbonate C43H59IN4O10 详情 详情
(XXXVI) 32450 (4R,7S,10S,16S,19S,25S,26R,27R)-10-(3-hydroxybenzyl)-19-[(E)-2-iodo-1-methylethenyl]-7-isopropyl-1,26-dimethyl-18,28,29-trioxa-6,9,12,30-tetraazatetracyclo[23.3.1.1(12,16).0(4,27)]triaconta-21,23-diene-5,8,11,17-tetrone; (4R,7S,10S,16S,19S,25S,26R,27R)-10-(3-hydroxybenzyl)-19-[(E)-2-iodo-1-methylethenyl]-7-isopropyl-1,26-dimethyl-18,28,29-trioxa-6,9,12,30-tetraazatetracyclo[23.3.1.1(12,16).0(4,27)]triaconta-21,23-diene-5,8,11,17-tetrone C38H51IN4O8 详情 详情
Extended Information