2-formyl-1,5-dimethoxy-6-(2'-oxopropyl)anthraquinone | 89414-68-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 2-formyl-1,5-dimethoxy-6-(2'-oxopropyl)anthraquinone
• 英文别名: 1,5-Dimethoxy-9,10-dioxo-6-(2-oxopropyl)anthracene-2-carbaldehyde
• CAS: 89414-68-6
• 化学式: C₂₀H₁₆O₆
• 分子量: 352.343
• InChiKey: BWKDGBWSZSOSQZ-UHFFFAOYSA-N

物化性质

• 沸点：
  587.7±50.0 °C(Predicted)
• 密度：
  1.328±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-formyl-1,5-dimethoxy-6-(2'-oxopropyl)anthraquinone 在 tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium sodium hydroxide 、 dimethyl sulfide borane 、 双氧水 、 三溴化硼 、 potassium carbonate 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 vineomycinone B2 methyl ester
  参考文献：
  名称：

  葡萄霉素B2苷元的全合成

  摘要：

  Synthese du compose du titre qui est l'acide dihydroxy-1,5 [dihydroxy-4,5methyl-6 perhydropyrannyl-2]-6 β-hydroxy β-methyl anthraquinonebutyrique-2

  DOI：

  10.1021/ja00320a049
• 作为产物：
  描述：

  5-羟基对萘醌 在 rhodium(III) chloride 、 二甲基硫 、 碳酸氢钠 、 potassium carbonate 、 臭氧 、 silver(l) oxide 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 2-formyl-1,5-dimethoxy-6-(2'-oxopropyl)anthraquinone
  参考文献：
  名称：

  葡萄霉素B2甲酯的全合成

  摘要：

  合成这些 faisant intervenir des siloxy diene avec deux 反应 homo-Diels Alder et une 反应hetero-Diels Alder

  DOI：

  10.1021/ja00291a031

文献信息

• Total synthesis of vineomycin B2 aglycon
  作者：Samuel Danishefsky、Biing Jiun Uang、George Quallich

  DOI：10.1021/ja00320a049

  日期：1984.4

  Synthese du compose du titre qui est l'acide dihydroxy-1,5 [dihydroxy-4,5 methyl-6 perhydropyrannyl-2]-6 β-hydroxy β-methyl anthraquinonebutyrique-2

  Synthese du compose du titre qui est l'acide dihydroxy-1,5 [dihydroxy-4,5methyl-6 perhydropyrannyl-2]-6 β-hydroxy β-methyl anthraquinonebutyrique-2
• Experiments Directed Towards the Synthesis of Anthracyclinones. XXXIV Hetero-Diels - Alder Reactions Using Chiral Boron and Titanium Reagents
  作者：Mark D. Bercich、Richard C. Cambie、Peter S. Rutledge

  DOI：10.1071/ch98181

  日期：——

  Reactions between benzaldehyde or o-anisaldehyde and a series of silyloxy dienes catalysed by the chiral acyl- oxyborane (CAB) complex (4) give high yields of enantioselective products from a Mukaiyama aldol rather than a hetero-Diels–Alder reaction. Attempts to effect a similar catalytic reaction with anthraquinone aldehydes were unsuccessful but use of 2 equiv. of the CAB complex (1) followed by cyclization promotes a formal hetero- Diels–Alder reaction between the aldehyde (7) and the diene (12) to give the dihydropyrone (24) in 45% yield and with a 79% e.e. in favour of the 2'R enantiomer. Hetero-Diels–Alder reactions between the aldehyde (7) and the diene (12) using the chiral titanium complexes Ti[(R)-BINOL]Cl 2 , Ti[(R,R)-TADDOL]Cl 2 and Ti[(R)-BINOL] 2 have been investigated. The first two complexes promote the reaction at −30 and −78° respectively but with low induced enantioselectivities.

  苯甲醛或邻甲氧基苯甲醛与一系列硅烷氧基二烯通过手性酰氧硼烷（CAB）配合物（4）催化反应，产生高收率的对向异构体产物，而不是杂环Diels-Alder反应。尝试使用蒽醌醛进行类似的催化反应失败，但使用2当量的CAB配合物（1）随后进行环化反应，促进了醛（7）和二烯（12）之间的形式杂环Diels-Alder反应，产生二氢吡喃（24），收率为45％，对2'R对映体有79％的对映选择性。使用手性钛配合物Ti [(R)-BINOL] Cl2，Ti [(R,R)-TADDOL] Cl2和Ti [(R)-BINOL] 2进行了醛（7）和二烯（12）之间的杂环Diels-Alder反应的研究。前两种配合物分别在-30℃和-78℃促进反应，但对映选择性较低。
• Experiments Directed Towards the Synthesis of Anthracyclinones. XXXII. Synthesis of Anthraquinone Aldehydes
  作者：Mark D. Bercich、Richard C. Cambie、Peter S. Rutledge

  DOI：10.1071/c98102

  日期：——

  Syntheses of C2 anthraquinone aldehydes from the commercially availableanthraru¯n (1) have been investigated. A synthesis of the keto aldehyde(2) in nine steps and 73% overall yield was achieved. Syntheses of (2)exploiting selective oxidations of either a C-boundallyl group by Wacker oxidation to introduce the methyl keto functionality orof a C-bound prop-1-enyl moiety by dihydroxylation andoxidative cleavage to generate the C2 formyl group were also developed. Thealdehyde (27) was synthesized in seven steps and in 81% overall yieldfrom (1), and syntheses of the phenolic aldehydes (33), (34), and (35), the C1benzyloxy aldehyde (36) and the anthracene aldehyde (37) were also developed.

  对商业可得到的蒽醌（1）进行了C2蒽醌醛的合成研究。通过九步反应，得到了酮醛（2），总产率为73%。还开发了利用Wacker氧化选择性氧化C-联苯丙基基团引入甲基酮基官能团或利用二羟基化和氧化解裂选择性氧化C-联丙烯基基团生成C2甲醛基团的（2）的合成方法。从（1）中，七步反应得到了醛（27），总产率为81％，并开发了酚醛（33）、（34）和（35）、C1苄氧基醛（36）和蒽醌醛（37）的合成方法。
• Experiments Directed Towards the Synthesis of Anthracyclinones. XXXIII. Hetero-Diels-Alder Reactions Using Togni's Catalyst
  作者：Mark D. Bercich、Richard C. Cambie、Peter S. Rutledge

  DOI：10.1071/c98150

  日期：——

  (+)-Bis[3-(heptafluorobutyryl)camphorato]oxovanadium(IV) [(+)-VO(hfc)2] (2) is an effective catalyst for the hetero-Diels-Alder reaction of a variety of anthraquinone aldehydes and silyloxy dienes giving high yields of cycloadducts. The reactions all proceed with strict endo topology giving rise to cis products; this indicates that they follow a similar mechanistic pathway to that proposed by Danishefsky for reactions catalysed by the europium complexes Eu(fod)3 and Eu(hfc)3. Reactions employing the dimethoxy aldehydes (3) and (4) and the phenolic aldehydes (5) and (6) proceed with only modest degrees of enantioselection. Reaction with the benzyloxy aldehyde (7) proceeds with significantly reduced enantioselectivity indicating that the nature of a substituent at C1 can have a significant effect. Enantioselectivity is generally higher for reactions at low temperature and when toluene rather than dichloromethane is used as solvent. The cycloadduct (24) has been elaborated to the anthracene C-glycoside (28) of known configuration, thereby establishing that the hetero-Diels-Alder reaction favours formation of the 2′R,6′R enantiomer of (24). This enantiofacial selectivity has been correlated with the sense of anisochrony observed in the 1H n.m.r. spectrum of the ketone (17), a derivative of (24), in the presence of the solvating agent (S)-(+)-trifluoroanthrylethanol [(S)-(+)-TFAE]. The enone (21) has been elaborated to the anthraquinone olivose C-glycoside (33), a synthesis demonstrating the utility of hetero-Diels-Alder reactions involving silyloxy dienes with terminal silyloxy or methyl substituents for such syntheses.

  (+)-双[3-(七氟丁酰基)樟脑]氧钒(IV) (+)-双[3-(七氟丁酰基)樟脑]氧钒(IV) (2)是一种有效的催化剂，可用于多种蒽醌醛和油酸酯的异狄尔斯-阿尔德反应。 醛和 silyloxy 二烯的杂-Diels-Alder 反应的有效催化剂，可产生高产率的环加载产物。反应 反应均以严格的内向拓扑结构进行，并产生顺式产物。 这表明它们遵循了 与 Danishefsky 为铕催化反应提出的机理途径相似。 铕配合物 Eu(fod)3 和 Eu(hfc)3。使用二甲氧基醛的反应 (3)和(4)以及酚醛(5)和(6)进行的反应只有适度的对映体选择。 对映体选择性较低。与苄氧基醛 (7) 反应的对映体选择性明显降低。 与苄氧基醛 (7) 的反应过程中，对映体选择性大大降低，这表明 C1 取代基的性质会产生重大影响。对映体选择性 通常在低温条件下以及使用甲苯而不是二氯甲烷时，对映体选择性更高。 二氯甲烷作为溶剂时，对映体选择性通常更高。环加载产物 (24) 已被详细阐述为 为已知构型的蒽 C-糖苷 (28)。 构型，从而确定了杂-Diels-Alder 反应 有利于形成 的 2′R、6′R 对映体。 (24).这种对映体选择性与 的 1H n.m.r. 光谱中观察到的异相性有关。 (24) 的衍生物酮 (17) 的 1H n.m.r 谱中观察到的异相性有关。 (S)-(+)-三氟蒽乙醇 [(S)-(+)-三氟蒽乙醇]。烯酮 (21) 合成了蒽醌橄榄糖 C-糖苷 (33)。 (33)，这一合成证明了杂环-Diels-Alder 反应的实用性。 该合成证明了涉及具有末端硅氧基或甲基取代基的硅氧基二烯的杂-Diels-Alder 反应在此类合成中的实用性。 这种合成证明了涉及具有末端硅氧基或甲基取代基的硅氧基二烯的杂
• Experiments Directed Towards the Synthesis of Anthracyclinones. XXV. Synthesis of a Vineomycinone B2 Methyl Ester Intermediate From Anthrarufin
  作者：MD Bercich、RC Cambie、TA Howe、PS Rutledge、SD Thomson、PD Woodgate

  DOI：10.1071/ch9950531

  日期：——

  6-(1'-Formyl)-1,5-dimethoxy-2-(2″-oxopropyl) anthraquinone (1), a key intermediate in Danishefsky's synthesis of vineomycinone B2 methyl ester (5), has been prepared by a new route from anthrarufin (6) via the intermediate 1-methoxy-2-(2′-methylprop-2′-enyl)-5-(2′-methylprop-2′-enyloxy) anthraquinone (20). An alternative synthesis of the diketone (40) has been achieved via Claisen rearrangement of (20) and a subsequent ozonolysis of the resulting bis ( methylpropenyl ) anthraquinone (26). Other routes to (1) from anthrarufin have been developed. In one, compound (1) was formed in yields of 10-16% as an anomalous product from the ozonolysis of (27). Ozonolyses of mixtures of (27), (37) and (44), obtained by isomerization of (27), afforded (1) in yields of 28-43%. Isomerization of the diphenol (25) with palladium(II) chloride bis ( acetonitrile ) in refluxing chloroform proceeds at a faster rate than the isomerization of (27), thereby affording the mono isomerized diphenol (38) in 37% yield. Methylation of (38) affords (37), a known precursor of (1).

  6-(1'-甲酰基)-1,5-二甲氧基-2-(2″-氧代丙基)蒽醌(1)是 Danishefsky 合成藤霉素酮 B2 甲酯(5)的关键中间体、通过中间体 1-甲氧基-2-(2′-甲基丙-2′-烯基)-5-(2′-甲基丙-2′-烯氧基)蒽醌(20)，以新的路线从蒽藜芦苷(6)制备得到。二酮(40)的另一种合成方法是通过(20)的克莱森重排，然后对生成的双(甲基丙烯基)蒽醌(26)进行臭氧分解。从蒽醌制取(1)的其他途径也已开发出来。其中，(27)的臭氧分解生成的化合物(1)是一种异常产物，产率为 10-16%。由 (27) 异构化得到的 (27)、(37) 和 (44) 混合物的臭氧分解生成了 (1)，产率为 28-43%。 二苯酚（25）与氯化钯（II）双（乙腈）在回流氯仿中的异构化速度比（27）的异构化速度快，从而得到单异构化的二苯酚（38），收率为 37%。将(38)甲基化可得到(37)，即已知的(1)前体。