methyl (1R,11R,12S,13R)-13-(hydroxymethyl)-11-(3,4,5-trimethoxyphenyl)-5,7,14-trioxatetracyclo[9.2.1.0(2,10).0(4,8)]tetradeca-2(10),3,8-triene-12-carboxylate -Drug Synthesis Database

【结构式】

【分子编号】35010

【品名】methyl (1R,11R,12S,13R)-13-(hydroxymethyl)-11-(3,4,5-trimethoxyphenyl)-5,7,14-trioxatetracyclo[9.2.1.0(2,10).0(4,8)]tetradeca-2(10),3,8-triene-12-carboxylate

【CA登记号】

【分子式】C₂₃H₂₄O₉

【分子量】444.43816

【元素组成】C 62.16% H 5.44% O 32.4%

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：(LX)

The cyclization of 6-[1-hydroxy-1-(3,4,5-trimethoxyphenyl)methyl]-1,3-benzodioxol-5-carbaldehyde dimethylacetal (LVI) by means of AcOH gives 5-(3,4,5-trimethoxyphenyl)-1,3-dioxolo[4,5-f]isobenzofuran (LVII), which is submitted to a Diels-Alder cyclization with acetylenedicarboxylic acid dimethyl ester (LVIII) yielding the epoxy derivative (LIX). The selective reduction of (LIX) with LiBEt3H and H2 affords the carbinol (LX), which is treated with H2 over RaNi in order to open the epoxide ring to give the diol (LXI) with the wrong configuration at the secondary OH group. The treatment of (LXI) with aqueous acid isomerizes the secondary OH group to (LXII) with the suitable configuration. Finally, this compound is cyclized with DCC to the desired target compound.

参考文献中间体

合成目标

【1】 Ward, R.S.; Synthesis of podophyllotoxin and related compounds. Synthesis 1992, 719.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(LVI)	35007	[6-(dimethoxymethyl)-1,3-benzodioxol-5-yl](3,4,5-trimethoxyphenyl)methanol		C₂₀H₂₄O₈	详情	详情
(LVII)	35008	4-furo[3,4-f][1,3]benzodioxol-5-yl-2,6-dimethoxyphenyl methyl ether; 5-(3,4,5-trimethoxyphenyl)furo[3,4-f][1,3]benzodioxole		C₁₈H₁₆O₆	详情	详情
(LVIII)	24551	Dimethyl acetylenedicarboxylate; Dimethyl 2-butynedioate;Acetylenedicarboxylic acid dimethyl ester	762-42-5	C₆H₆O₄	详情	详情
(LIX)	35009	dimethyl (1R,11S)-1-(3,4,5-trimethoxyphenyl)-5,7,14-trioxatetracyclo[9.2.1.0(2,10).0(4,8)]tetradeca-2(10),3,8,12-tetraene-12,13-dicarboxylate		C₂₄H₂₂O₁₀	详情	详情
(LX)	35010	methyl (1R,11R,12S,13R)-13-(hydroxymethyl)-11-(3,4,5-trimethoxyphenyl)-5,7,14-trioxatetracyclo[9.2.1.0(2,10).0(4,8)]tetradeca-2(10),3,8-triene-12-carboxylate		C₂₃H₂₄O₉	详情	详情
(LXI)	35011	methyl (5R,6R,7R,8S)-8-hydroxy-7-(hydroxymethyl)-5-(3,4,5-trimethoxyphenyl)-5,6,7,8-tetrahydronaphtho[2,3-d][1,3]dioxole-6-carboxylate		C₂₃H₂₆O₉	详情	详情
(LXII)	35012	(5R,6R,7R,8R)-8-hydroxy-7-(hydroxymethyl)-5-(3,4,5-trimethoxyphenyl)-5,6,7,8-tetrahydronaphtho[2,3-d][1,3]dioxole-6-carboxylic acid		C₂₂H₂₄O₉	详情	详情

Extended Information