dimethyl (E)-2-butenylboronate -Drug Synthesis Database

【结构式】

【分子编号】47484

【品名】dimethyl (E)-2-butenylboronate

【CA登记号】

【分子式】C₆H₁₃BO₂

【分子量】127.97902

【元素组成】C 56.31% H 10.24% B 8.45% O 25%

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：(VI)

The reaction of the chiral epoxide (I) with 4-methoxybenzaldehyde (II) by means of NaAl(OMe)3H in THF gives the 1,3-dioxane (III), which is opened by reduction with DIBAL in dichloromethane to yield the chiral benzyl ether (IV). The oxidation of the primary alcohol of (IV) with DMP in dichloromethane affords the corresponding aldehyde (V), which is condensed with the boronate (VI) and S,S-diisopropyl tartrate in toluene to provide the unsaturated alcohol (VII).The protection of (VII) with Tbdps-Cl and imidazole yields the fully protected triol (VIII), which is oxidized at the terminal double bond with 9-BBN in THF to give the primary alcohol (IX). The oxidation of (IX) with DMP in dichloromethane affords the aldehyde (X), which is condensed with methylenetriphenylphosphorane (XI) in THF to provide the terminal olefin (XII). Elimination of the Pmb protecting group of (XII) with DDQ in dichloromethane gives the alcohol (XIII), which is esterified with 2-allyl-6-methoxybenzoic acid (XIV)(obtained by allylation of 2-methoxybenzoic acid (XV) with allyl bromide (XVI), BuLi and MgBr2) by means of DEAD and PPh3 yielding the ester (XVII). The cyclization of (XVII) by means of a metathesis reaction catalyzed by a ruthenium catalyst in refluxing dichloromethane affords the bicyclic lactone (XVIII), which is treated with BBr3 in dichloromethane to provide the dihydroxylated lactone (XIX).

参考文献中间体

合成目标

【1】 Labrecque, D.; et al.; Enantioselective total synthesis of salicylihalamides A and B. Tetrahedron Lett 2001, 42, 14, 2645.

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)	47480	[(2R,3R)-3-[3-(benzyloxy)propyl]oxiranyl]methanol		C₁₃H₁₈O₃	详情	详情
(II)	27251	4-methoxybenzaldehyde; Anisicaldehyde; p-anisaldehyde	123-11-5	C₈H₈O₂	详情	详情
(III)	47481	(4R)-4-[3-(benzyloxy)propyl]-2-(4-methoxyphenyl)-1,3-dioxane; benzyl 3-[(4R)-2-(4-methoxyphenyl)-1,3-dioxan-4-yl]propyl ether		C₂₁H₂₆O₄	详情	详情
(IV)	47482	(3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]-1-hexanol		C₂₁H₂₈O₄	详情	详情
(V)	47483	(3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]hexanal		C₂₁H₂₆O₄	详情	详情
(VI)	47484	dimethyl (E)-2-butenylboronate		C₆H₁₃BO₂	详情	详情
(VII)	47485	(3S,4R,6R)-9-(benzyloxy)-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonen-4-ol		C₂₅H₃₄O₄	详情	详情
(VIII)	47486	[((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-3-butenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-8-nonenyl ether		C₄₁H₅₂O₄Si	详情	详情
(IX)	47487	(3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonanol		C₄₁H₅₄O₅Si	详情	详情
(X)	47488	(3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methylnonanal		C₄₁H₅₂O₅Si	详情	详情
(XI)	27301	methylene(triphenyl)phosphorane		C₁₉H₁₇P	详情	详情
(XII)	47489	[((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-4-pentenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-9-decenyl ether		C₄₂H₅₄O₄Si	详情	详情
(XIII)	47490	(4R,6R,7S)-1-(benzyloxy)-6-[[tert-butyl(diphenyl)silyl]oxy]-7-methyl-9-decen-4-ol		C₃₄H₄₆O₃Si	详情	详情
(XIV)	13926	2-Methoxybenzoic acid; o-Methoxybenzoic Acid	579-75-9	C₈H₈O₃	详情	详情
(XV)	11463	3-Bromo-1-propene; 3-Bromopropene；allyl bromide	106-95-6	C₃H₅Br	详情	详情
(XVI)	47491	2-allyl-6-methoxybenzoic acid		C₁₁H₁₂O₃	详情	详情
(XVII)	47492	(1S,3R,4S)-1-[3-(benzyloxy)propyl]-3-[[tert-butyl(diphenyl)silyl]oxy]-4-methyl-6-heptenyl 2-allyl-6-methoxybenzoate		C₄₅H₅₆O₅Si	详情	详情
(XVIII)	47493	(3S,5R,6S)-3-[3-(benzyloxy)propyl]-5-[[tert-butyl(diphenyl)silyl]oxy]-14-methoxy-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one		C₄₃H₅₂O₅Si	详情	详情
(XIX)	47494	(3S,5R,6S)-5-[[tert-butyl(diphenyl)silyl]oxy]-14-hydroxy-3-(3-hydroxypropyl)-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one		C₃₅H₄₄O₅Si	详情	详情

合成路线2

该中间体在本合成路线中的序号：(VI)

参考文献中间体

合成目标

【1】 Labrecque, D.; et al.; Enantioselective total synthesis of salicylihalamides A and B. Tetrahedron Lett 2001, 42, 14, 2645.

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)	47480	[(2R,3R)-3-[3-(benzyloxy)propyl]oxiranyl]methanol		C₁₃H₁₈O₃	详情	详情
(II)	27251	4-methoxybenzaldehyde; Anisicaldehyde; p-anisaldehyde	123-11-5	C₈H₈O₂	详情	详情
(III)	47481	(4R)-4-[3-(benzyloxy)propyl]-2-(4-methoxyphenyl)-1,3-dioxane; benzyl 3-[(4R)-2-(4-methoxyphenyl)-1,3-dioxan-4-yl]propyl ether		C₂₁H₂₆O₄	详情	详情
(IV)	47482	(3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]-1-hexanol		C₂₁H₂₈O₄	详情	详情
(V)	47483	(3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]hexanal		C₂₁H₂₆O₄	详情	详情
(VI)	47484	dimethyl (E)-2-butenylboronate		C₆H₁₃BO₂	详情	详情
(VII)	47485	(3S,4R,6R)-9-(benzyloxy)-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonen-4-ol		C₂₅H₃₄O₄	详情	详情
(VIII)	47486	[((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-3-butenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-8-nonenyl ether		C₄₁H₅₂O₄Si	详情	详情
(IX)	47487	(3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonanol		C₄₁H₅₄O₅Si	详情	详情
(X)	47488	(3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methylnonanal		C₄₁H₅₂O₅Si	详情	详情
(XI)	27301	methylene(triphenyl)phosphorane		C₁₉H₁₇P	详情	详情
(XII)	47489	[((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-4-pentenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-9-decenyl ether		C₄₂H₅₄O₄Si	详情	详情
(XIII)	47490	(4R,6R,7S)-1-(benzyloxy)-6-[[tert-butyl(diphenyl)silyl]oxy]-7-methyl-9-decen-4-ol		C₃₄H₄₆O₃Si	详情	详情
(XIV)	13926	2-Methoxybenzoic acid; o-Methoxybenzoic Acid	579-75-9	C₈H₈O₃	详情	详情
(XV)	11463	3-Bromo-1-propene; 3-Bromopropene；allyl bromide	106-95-6	C₃H₅Br	详情	详情
(XVI)	47491	2-allyl-6-methoxybenzoic acid		C₁₁H₁₂O₃	详情	详情
(XVII)	47492	(1S,3R,4S)-1-[3-(benzyloxy)propyl]-3-[[tert-butyl(diphenyl)silyl]oxy]-4-methyl-6-heptenyl 2-allyl-6-methoxybenzoate		C₄₅H₅₆O₅Si	详情	详情
(XVIII)	47493	(3S,5R,6S)-3-[3-(benzyloxy)propyl]-5-[[tert-butyl(diphenyl)silyl]oxy]-14-methoxy-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one		C₄₃H₅₂O₅Si	详情	详情
(XIX)	47494	(3S,5R,6S)-5-[[tert-butyl(diphenyl)silyl]oxy]-14-hydroxy-3-(3-hydroxypropyl)-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one		C₃₅H₄₄O₅Si	详情	详情

Extended Information