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【结 构 式】

【分子编号】61706

【品名】tert-butyl(dimethyl)silyl (1R,2S)-1-{[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]methyl}-2-methyl-3-butenyl ether; tert-butyl[((1R,2S)-1-{[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]methyl}-2-methyl-3-butenyl)oxy]dimethylsilane

【CA登记号】

【 分 子 式 】C19H38O3Si

【 分 子 量 】342.59442

【元素组成】C 66.61% H 11.18% O 14.01% Si 8.2%

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:(IV)

The condensation of aldehyde (I) with boronate (II) in toluene gives the chiral alcohol (III), which is treated with Tbdms-OTf and TEA to yield the silyl ether (IV). The hydroxylation of the terminal double bond of (IV) by means of 9-BBN in refluxing THF affords the primary alcohol (V), which is oxidized by means of the Swern oxidant to provide the aldehyde (VI). The homologation of (VI) with methyltriphenylphosphonium iodide (VII) and NaHMDS gives the unsaturated compound (VIII), which is deprotected at the ketonide group by means of TFA in dichloromethane to afford the diol (IX). The dehydration of (IX) by means of tosylimidazole (X) and NaH in THF provides the epoxide (XI), which is condensed with the Grignard reagent (XIII) (obtained by reaction of the tributyltin derivative (XII) with MgBr2) to give the secondary alcohol (XIV). The reaction of 2-allyl-6-methoxybenzamide (XV) with I2 in THF/water gives the lactone (XVI), which is treated with Zn and AcOH to yield 2-allyl-6-methoxybenzoic acid (XVII). The esterification of acid (XVII) with alcohol (XIV) by means of DEAD and PPH3 affords the corresponding ester (XVIII), which is submitted to a ring closing metathesis reaction by means of a Ru catalyst to provide the macrolactone (XIX). The cleavage of the Pmb protecting group of (XIX) by means of DDQ gives the primary alcohol (XX), which is oxidized to the aldehyde (XXI) by means of DMP oxidant.

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 CAS号 分子式 供应商 用于合成
(I) 61703 2-[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]acetaldehyde C9H16O3 详情 详情
(II) 61704 diisopropyl (4S,5S)-2-[(E)-2-butenyl]-1,3,2-dioxaborolane-4,5-dicarboxylate C14H23BO6 详情 详情
(III) 61705 (2R,3S)-1-[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]-3-methyl-4-penten-2-ol C13H24O3 详情 详情
(IV) 61706 tert-butyl(dimethyl)silyl (1R,2S)-1-{[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]methyl}-2-methyl-3-butenyl ether; tert-butyl[((1R,2S)-1-{[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]methyl}-2-methyl-3-butenyl)oxy]dimethylsilane C19H38O3Si 详情 详情
(V) 61707 (3S,4R)-4-{[tert-butyl(dimethyl)silyl]oxy}-5-[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]-3-methyl-1-pentanol C19H40O4Si 详情 详情
(VI) 61708 (3S,4R)-4-{[tert-butyl(dimethyl)silyl]oxy}-5-[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]-3-methylpentanal C19H38O4Si 详情 详情
(VII) 13484 Methyl(triphenyl)phosphonium iodide; Methyltriphenylphosphonium iodide 2065-66-9 C19H18IP 详情 详情
(VIII) 61709 tert-butyl(dimethyl)silyl (1R,2S)-1-{[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]methyl}-2-methyl-4-pentenyl ether; tert-butyl[((1R,2S)-1-{[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]methyl}-2-methyl-4-pentenyl)oxy]dimethylsilane C20H40O3Si 详情 详情
(IX) 61710 (2S,4R,5S)-4-{[tert-butyl(dimethyl)silyl]oxy}-5-methyl-7-octene-1,2-diol C15H32O3Si 详情 详情
(X) 47846 1-[(4-methylphenyl)sulfonyl]-1H-imidazole 2232-08-8 C10H10N2O2S 详情 详情
(XI) 61711 tert-butyl(dimethyl)({(1R,2S)-2-methyl-1-[(2S)oxiranylmethyl]-4-pentenyl}oxy)silane; tert-butyl(dimethyl)silyl (1R,2S)-2-methyl-1-[(2S)oxiranylmethyl]-4-pentenyl ether C15H30O2Si 详情 详情
(XII) 61712 tributyl{(E)-3-[(4-methoxybenzyl)oxy]-1-propenyl}stannane; 4-methoxybenzyl (E)-3-(tributylstannyl)-2-propenyl ether C23H40O2Sn 详情 详情
(XIII) 61713 bromo{(E)-3-[(4-methoxybenzyl)oxy]-1-propenyl}magnesium C11H13BrMgO2 详情 详情
(XIV) 61716 (2E,5R,7R,8S)-7-{[tert-butyl(dimethyl)silyl]oxy}-1-[(4-methoxybenzyl)oxy]-8-methyl-2,10-undecadien-5-ol C26H44O4Si 详情 详情
(XV) 61714 2-allyl-6-methoxy-N,N-dipropylbenzamide C17H25NO2 详情 详情
(XVI) 61715 3-(iodomethyl)-8-methoxy-3,4-dihydro-1H-isochromen-1-one C11H11IO3 详情 详情
(XVII) 47491 2-allyl-6-methoxybenzoic acid C11H12O3 详情 详情
(XVIII) 61717 (1S,3R,4S)-3-{[tert-butyl(dimethyl)silyl]oxy}-1-{(E)-4-[(4-methoxybenzyl)oxy]-2-butenyl}-4-methyl-6-heptenyl 2-allyl-6-methoxybenzoate C37H54O6Si 详情 详情
(XIX) 61718 (3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-methoxy-3-{(E)-4-[(4-methoxybenzyl)oxy]-2-butenyl}-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one C35H50O6Si 详情 详情
(XX) 61719 (3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-3-[(E)-4-hydroxy-2-butenyl]-14-methoxy-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one C27H42O5Si 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
Extended Information