methyl 4-(tributylstannyl)benzoate -Drug Synthesis Database

【结构式】

【分子编号】32523

【品名】methyl 4-(tributylstannyl)benzoate

【CA登记号】

【分子式】C₂₀H₃₄O₂Sn

【分子量】425.19876

【元素组成】C 56.5% H 8.06% O 7.53% Sn 27.92%

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：(XII)

Triflate (XI) was coupled with methyl 4-(tributylstannyl)benzoate (XII) using Pd2(dba)3 and Ph3As to introduce the benzoate side-chain yielding (XIII). Benzylic oxidation of (XIII) with tert-butyl hydroperoxide and pyridinium dichromate provided anthracenone (XIV). Optionally, this was converted to vinyl triflate (XV) by means of trifluoromethanesulfonic anhydride and 2,6-di-tert-butyl-4-methylpyridine (DTBMP). Addition of Grignard reagent (XVI) to ketone (XIV), followed by acid dehydration of the resulting carbinol (XVIII) furnished the diaryl anthracene (XVIII). In an alternative procedure intermediate (XVIII) was prepared by Stille coupling of vinyl triflate (XV) with 3-methyl tributylstannylbenzene (XIX). Finally, the title carboxylic acid was obtained by saponification of the ester group of (XIX) with KOH.

参考文献中间体

合成目标

【1】 Ericsson, A.; Marinier, A.; Lapointe, P.; et al.; Synthesis and SAR of novel dihydroanthracene derivatives as retinoid analogs. 218th ACS Natl Meet (Aug 22 1999, New Orleans) 1999, Abst MEDI 43.
【2】 Starrett, J.E. Jr.; Tramposch, K.M.; Martel, A.; Nair, X.; Zusi, F.C.; Reczek, P.R.; Marinier, A.; Ericsson, A. (Bristol-Myers Squibb Co.); Retinoid-like cpds.. WO 9849136 .

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XI)	32522	5,5-dimethyl-5,6,7,8-tetrahydro-2-anthracenyl trifluoromethanesulfonate	C₁₇H₁₇F₃O₃S	详情	详情
(XII)	32523	methyl 4-(tributylstannyl)benzoate	C₂₀H₃₄O₂Sn	详情	详情
(XIII)	32524	methyl 4-(5,5-dimethyl-5,6,7,8-tetrahydro-2-anthracenyl)benzoate	C₂₄H₂₄O₂	详情	详情
(XIV)	32525	methyl 4-(5,5-dimethyl-8-oxo-5,6,7,8-tetrahydro-2-anthracenyl)benzoate	C₂₄H₂₂O₃	详情	详情
(XV)	32526	methyl 4-(5,5-dimethyl-8-[[(trifluoromethyl)sulfonyl]oxy]-5,6-dihydro-2-anthracenyl)benzoate	C₂₅H₂₁F₃O₅S	详情	详情
(XVI)	32527	bromo(3-methylphenyl)magnesium	C₇H₇BrMg	详情	详情
(XVII)	32528	methyl 4-[8-hydroxy-5,5-dimethyl-8-(3-methylphenyl)-5,6,7,8-tetrahydro-2-anthracenyl]benzoate	C₃₁H₃₀O₃	详情	详情
(XVIII)	32529	methyl 4-[5,5-dimethyl-8-(3-methylphenyl)-5,6-dihydro-2-anthracenyl]benzoate	C₃₁H₂₈O₂	详情	详情
(XIX)	32530	tributyl(3-methylphenyl)stannane	C₁₉H₃₄Sn	详情	详情

合成路线2

该中间体在本合成路线中的序号：(XII)

Triflate (XI) was coupled with methyl 4-(tributylstannyl)benzoate (XII) using Pd2(dba)3 and Ph3As to introduce the benzoate side-chain yielding (XIII). Benzylic oxidation of (XIII) with tert-butyl hydroperoxide and pyridinium dichromate provided anthracenone (XIV), which was converted to vinyl triflate (XV) by means of trifluoromethanesulfonic anhydride and 2,6-di-tert-butyl-4-methylpyridine (DTBMP). Diaryl anthracene (XVII) was prepared by Stille coupling of triflate (XV) with 3-acetoxytributylstannylbenzene (XVI). Finally, the title carboxylic acid was obtained by saponification of both ester groups of (XVII) by means of KOH.

参考文献中间体

合成目标

【1】 Ericsson, A.; Marinier, A.; Lapointe, P.; et al.; Synthesis and SAR of novel dihydroanthracene derivatives as retinoid analogs. 218th ACS Natl Meet (Aug 22 1999, New Orleans) 1999, Abst MEDI 43.
【2】 Starrett, J.E. Jr.; Tramposch, K.M.; Martel, A.; Nair, X.; Zusi, F.C.; Reczek, P.R.; Marinier, A.; Ericsson, A. (Bristol-Myers Squibb Co.); Retinoid-like cpds.. WO 9849136 .

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XI)	32522	5,5-dimethyl-5,6,7,8-tetrahydro-2-anthracenyl trifluoromethanesulfonate	C₁₇H₁₇F₃O₃S	详情	详情
(XII)	32523	methyl 4-(tributylstannyl)benzoate	C₂₀H₃₄O₂Sn	详情	详情
(XIII)	32524	methyl 4-(5,5-dimethyl-5,6,7,8-tetrahydro-2-anthracenyl)benzoate	C₂₄H₂₄O₂	详情	详情
(XIV)	32525	methyl 4-(5,5-dimethyl-8-oxo-5,6,7,8-tetrahydro-2-anthracenyl)benzoate	C₂₄H₂₂O₃	详情	详情
(XV)	32526	methyl 4-(5,5-dimethyl-8-[[(trifluoromethyl)sulfonyl]oxy]-5,6-dihydro-2-anthracenyl)benzoate	C₂₅H₂₁F₃O₅S	详情	详情
(XVI)	32531	3-(tributylstannyl)phenyl acetate	C₂₀H₃₄O₂Sn	详情	详情
(XVII)	32532	methyl 4-[8-[3-(acetoxy)phenyl]-5,5-dimethyl-5,6-dihydro-2-anthracenyl]benzoate	C₃₂H₂₈O₄	详情	详情

Extended Information