1-(dimethoxymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo<2.2.1>heptane | 98202-88-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: 1-(dimethoxymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo<2.2.1>heptane
• 英文别名: 1-(Dimethoxymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane
• CAS: 98202-88-1
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: JHVXPLHLONDBBM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(dimethoxymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo<2.2.1>heptane 在 4-二甲氨基吡啶 、 sodium hydroxide 作用下， 以 乙醚 、 乙醇 、 水 为溶剂， 反应 50.17h， 生成 (2R,5S,12R)-2-acetyl-5-(dimethoxymethyl)-2-hydroxy-1,2,3,4,5,12-hexahydro-5,12-epoxynaphthacen-2-yl 3-(4'-methoxyphenyl)prop-2-enoate
  参考文献：
  名称：

  Asymmetric Synthesis and DNA Intercalation of (−)-6-[[(Aminoalkyl)oxy]methyl]-4-demethoxy-6,7- dideoxydaunomycinones^1,

  摘要：

  The BP3 . Et(2)O-promoted Diels-Alder addition of 1-acetylvinyl RADO(Et)-ate (RADO(Et)-ate = 3-ethyl-2-oxo-6,8-dioxa-3-azabicylo[3.2.1]octane-7-exo-carboxylate) to 1-(dimethosymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane led to one major monoadduct that added to 1,2-didehydrobenzene and was converted into (-)-4-demethoxy-7-deoxydaunomycinone and (2R)-12-acetoxy-2-acetyl-5-(bromomethyl)-1,2,3,4-tetrahydronaphthacen-2-yl RADO(Et)-ate. The latter compound was used to construct (8R)-8-acetyl-6,8-dihydroxy-11-[[(3'-[(aminopropyl)oxy]-, -4'-[(aminobutyl)oxy], and -5'-[(aminopenty)oxy]methyl]-7,8,9,10-tetrahydronaphthacene-5,12-dione hydrochloride (-)-8, (-)-9, (-)-10, respectively, as well as (8R)-8-acetyl-6,8-dihydroxy-11-[[[2'-[(3 ''-aminopropyl)amino]ethyl]oxy]-((-)-11) and -[[[3'-[(3 ''-aminopropyl)amino]propyl]oxy]methyl]7,8,9,10--tetrahydronaphthacene-5,12-dione hydrochloride ((-)-12). (8R)-8-Acetyl-6,8-dihydroxy-11-[[(alpha-L-diaunosaminyl)oxy]methyl]-7,8,9,10-tetrahydronaphthacene-5,12-dione hydrachloride ((-)-13), a mimic of idarubicin, was also prepared. Absorbance and fluorescence titration experiments showed (-)-8, (-)-9, and (-)-10 to intercalate calf thymus DNA whereas (-)-11, (-)-12, and (-)-13 did not. The best intercalator was (-)-9 (K-b = (1.1 +/- 0.1) x 10(5) M(-1)) with the [(4'-aminobutyl)oxy]-methyl chain. Inhibition of topoisomerase II-induced DNA strand religation wats observed for (-)-8 at a concentration of 50 mu M.

  DOI：

  10.1021/jo960606z
• 作为产物：
  描述：

  [(2R,3S,5R,6S)-4-(dimethoxymethyl)-3,5,6-tris(methylsulfonyloxymethyl)-7-oxabicyclo[2.2.1]heptan-2-yl]methyl methanesulfonate 、 potassium tert-butylate 以60%的产率得到
  参考文献：
  名称：

  METRAL J. -L.; LAUTERWEIN J.; VOGEL P., HELV. CHIM. ACTA, 69,(1986) N 6, 1287-1309

  摘要：

  DOI：

文献信息

• Remote substituent effect on the electrophilic additions of 1,3-dienes. Synthesis of (2R)-5-(acetoxymethyl)-2-acetyl-1,2,3,4-tetrahydro-10-methoxynaphthacene-2,12-diyl diacetate
  作者：Hervé Mosimann、Zoltán Dienes、Pierre Vogel

  DOI：10.1016/0040-4020(95)00317-2

  日期：1995.6

  5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane (4) is highly regioselective giving 2-(chloromethyl)-1-(dimethoxymethyl)-5,6-dimethylidene-3-[(2-nitrophenylthio)methyl]-7-oxabicyclo[2.2.1]hept-2-ene (9). The reaction of 2-nitrobenzene-sulfenyl chloride with 8-(dimethoxymethyl)-9,10-dimethylidene-11-oxatricyclo[6.2.1.02,7]undec-2(7)-en-4-yl methyl ketone derivatives (5, (-)-6) was also regioselective

  向1-（二甲氧基甲基）-2,3,5,6-四亚甲基-7-氧杂双环[2.2.1]庚烷（4）中添加一当量的2-硝基苯亚磺酰氯是高度区域选择性的，得到2-（氯甲基）-1 -（二甲氧基甲基）-5，6-二甲基-3-[（2-硝基苯硫基）甲基] -7-氧杂双环[2.2.1]庚-2-烯（9）。2-硝基苯-亚磺酰氯与8-（二甲氧基甲基）-9,10-二甲叉基-11-氧三环的反应[6.2.1.0 2,7] undec-2（7）-en-4-yl甲基酮衍生物（5，（-）-6）也具有区域选择性，可得到1,2-取代的混合物，而不是竞争性马尔可夫尼可夫和反马尔可夫尼可夫产生的1,4-加合物在加成方式中，距离8-二甲氧基甲基取代基最远的烯烃部分是优选的。这些加合物经历了碱诱导的消除反应，形成了环硫基和氯取代的二烯，这些环加到2,3-二氢苯并茴香醚中，从而生成了由高度“邻位”区域选择性Diels-Alder添加得到的产物。无论
• Enantioselective synthesis of (R)-(−)-2-acetyl-2,5,12-trihydro-1,2,3,4-tetrahydro-6,11-naphthacenequinone via diastereoselective diels-alder cycloaddition
  作者：Zoltán Dienes、Thomas Antonsson、Pierre Vogel

  DOI：10.1016/s0040-4039(00)77479-x

  日期：1993.2

  The BF3·Et2O-promoted Diels-Alder addition of 1-acetylvinyl (1′R,5′S,7′R)-3′-ethyl-2′-oxo-3′-aza-6′,8′-dioxabicylo[3.2.1]octane-7′-carboxylate (1-acetylvinylRADO(Et)) to 1-(dimethoxymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1] heptane was highly regio-, stereo and diastereoselective giving a monoadduct that was converted into (R)-(−)-4-demethoxy-7-deoxydaunomycinone.

  BF 3 ·Et 2 O促进的1-乙酰乙烯基（1'R，5'S，7'R）-3'-乙基-2'-oxo-3'-aza-6'，8的Diels-Alder加成反应′-二氧杂双环[3.2.1]辛烷-7′-羧酸盐（1-乙酰基乙烯基RADO（Et））变成1-（二甲氧基甲基）-2,3,5,6-四亚甲基-7-氧杂环[2.2.1]庚烷区域，立体和非对映选择性，得到一加合物，将其转变为（R）-（-）-4-demethoxy-7-deoxydaunomycinone。
• Regioselectivity of 7-oxabicyclo[2.2.1]hepta-2,5-diene-phenol rearrangement as a function of the acid promoter. Stereoselective synthesis of 1,2,3,4-tetrahydro-2-hydroxynaphthalen-2-yl methyl ketones.
  作者：Thomas Antonsson、Pierre Vogel

  DOI：10.1016/s0040-4039(00)94341-7

  日期：1990.1

  p-nitrobenzoate and didehydrobenzene to 1-(dimethoxymethyl)-2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1] heptane led to 5-(dimethoxymethyl)-5,12-epoxy-2-(p-nitrobenzoyloxy)-l,2,3,4-tetrahydronaphthacen-2-yl methyl ketone with high regio- and stereoselectivity. The regioselectivity of the ethereal ring opening of the 7-oxanorbornadiene moiety of the latter compound depended on the Lewis acid promotor.

  将1-乙酰基乙烯基对硝基苯甲酸酯和二氢苯连续添加到1-（二甲氧基甲基）-2,3,5,6-四亚甲基-7-氧杂环[2.2.1]庚烷中的Diels-Alder加成反应生成5-（二甲氧基甲基）-5，具有高区域和立体选择性的12-环氧-2-（对硝基苯甲酰氧基）-1,2,3,4-四氢萘并-2-基甲基酮。后一种化合物的7-氧杂降冰片二烯部分的醚环开环的区域选择性取决于路易斯酸促进剂。
• ANTONSSON, THOMAS;VOGEL, PIERRE, TETRAHEDRON LETT., 31,(1990) N, C. 89-92
  作者：ANTONSSON, THOMAS、VOGEL, PIERRE

  DOI：——

  日期：——
• METRAL, J. -L.;VOGEL, P., HELV. CHIM. ACTA, 1985, 68, N 2, 334-337
  作者：METRAL, J. -L.、VOGEL, P.

  DOI：——

  日期：——