prop-2-enyl N-(6,6-dimethoxy-3-oxocyclohexa-1,4-dien-1-yl)carbamate | 157097-82-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: prop-2-enyl N-(6,6-dimethoxy-3-oxocyclohexa-1,4-dien-1-yl)carbamate
• CAS: 157097-82-0
• 化学式: C₁₂H₁₅NO₅
• 分子量: 253.255
• InChiKey: FNYRWDRFVIJFGE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  73.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  prop-2-enyl N-(6,6-dimethoxy-3-oxocyclohexa-1,4-dien-1-yl)carbamate 在 咪唑 、 4-二甲氨基吡啶 、 bis-triphenylphosphine-palladium(II) chloride 、 sodium tetrahydroborate 、 双氧水 、 三正丁基氢锡 、 4-甲基苯磺酸吡啶 、 potassium carbonate 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 116.5h， 生成 (2SR,3RS,4RS)-6-acetamido-4-(tert-butyldiphenylsilyloxy)-2,3-epoxycyclohex-5-enone
  参考文献：
  名称：

  Synthesis of (-)-LL-C10037α and Related Manumycin-Type Epoxyquinols

  摘要：

  以 N-烯丙氧基羰基保护的 2,5-二甲氧基苯胺为起点，通过高价碘氧化规程和选择性烯酮环氧化反应，九步即可得到链霉菌代谢物 LL-C10037δ，总收率为 7-10%。在这一策略的不对称变体中，(R,R)-戊烷-2,4-二醇被用作手性缩醛剂。由于正己胺基取代基限制了 1,3-二恶烷环的构象，由此产生的半醌螺缩醛进行了面选择性环氧化，并进一步官能化，得到了 (-)-LL-C10037 δ，ee 为 94%。这些方法首次合成了马诺霉素的高官能化 mC7N 核心，并进一步扩展到制备类似物，用于该类抗肿瘤抗生素的 SAR 研究。马努霉素能抑制 PFTase（蛋白法尼基转移酶）对 Ras 蛋白的法尼基化。

  DOI：

  10.1055/s-1995-4141
• 作为产物：
  描述：

  在 溶剂黄146 、 丙酮 作用下， 生成 prop-2-enyl N-(6,6-dimethoxy-3-oxocyclohexa-1,4-dien-1-yl)carbamate
  参考文献：
  名称：

  A new NF-κB inhibitor based on the amino-epoxyquinol core of DHMEQ

  摘要：

  The amino-epoxyquinols 6a and 6b were synthesized as soluble derivatives of an NF-kappa B inhibitor DHMEQ (1). In spite of the opposite configuration from 1, 6b rather than 6a affected the deactivation of NF-kappa B, based on NO secretion and MALDI-TOF MS analysis. It was indicated that 6b inhibited the activation by different manner from that of 1. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2010.08.036

文献信息

• Unique ring expansion of a 6-3 bicyclic ring system forming a functionalized 7-membered ring accelerated by nitrogen functional groups
  作者：Eiko Yasui、Rio Ootsuki、Kan Takayama、Shinji Nagumo

  DOI：10.1016/j.tetlet.2017.06.061

  日期：2017.8

  acid esters and (2-hydroxy-5-oxobicyclo [4.1.0] hept-3-en-3-yl) benzamide with TMSCl gave 7-membered ring compounds in good yields. The structure of the substituent at the C3 position of the cyclohexene ring is crucial for this ring expansion. The reaction mechanism is thought to involve the formation of a norcaradiene (bicyclo [4.1.0] hept-2,4-diene) structure and subsequent electrocyclic reaction.

  （2-羟基-5-氧代双环[4.1.0]庚-3-烯-3-基）氨基甲酸酯和（2-羟基-5-氧代双环[4.1.0]庚-3-烯-3的处理氨基苯甲酰胺与TMSC1的收率很好，得到了7元环化合物。环己烯环的C3位置的取代基结构对于该环的扩展至关重要。据认为，该反应机理涉及降正丁二烯（双环[4.1.0]庚-2，4-二烯）结构的形成和随后的电环反应。
• Synthesis and Evaluation of a Cyclopropane Derivative of DHMEQ
  作者：Eiko Yasui、Kan Takayama、Takahiro Nakago、Nobuyuki Takeda、Yasutada Imamura、Shinji Nagumo

  DOI：10.1248/cpb.c13-00914

  日期：——

  We have synthesized an analog 4 containing a cyclopropanated quinol skeleton and examined its ability to inhibit NF-κB. Surprisingly, 4 showed no remarkable NF-κB inhibitory activity as determined through expression of cyclooxygenase-2 (COX-2) in an RAW264.7 macrophage cell line.

  众所周知，脱羟甲基环氧喹诺霉素（DHMEQ，1）可抑制核因子-κB（NF-κB），后者与免疫，炎症和凋亡过程密切相关，是一种可诱导的转录因子。抑制作用似乎是环氧化物1与p65的Cys（38）开环的结果。我们合成了含有环丙烷基喹诺酮骨架的类似物4，并研究了其抑制NF-κB的能力。出乎意料的是，通过在RAW264.7巨噬细胞系中表达环氧合酶-2（COX-2）来确定，4没有显示出明显的NF-κB抑制活性。
• Synthesis of the Antitumor Antibiotic LL-C10037.alpha.
  作者：Peter Wipf、Yuntae Kim

  DOI：10.1021/jo00092a004

  日期：1994.7

  (+/-)-LL-C10037 alpha and its C(4)-epimer were prepared in nine steps from 2,5-dimethoxyaniline. The concise synthetic route represents the first synthesis of this highly functionalized antitumor antibiotic and is useful for the preparation of analogs of the putative pharmacophore of the Ras farnesyltransferase inhibitor manumycin.

  (+/-)-LL-C10037 顺式及其 C(4) 异构体，是从 2,5-二甲氧基苯胺开始，经过九步合成得到的。这一简洁的合成路线代表了这一高度官能团化的抗肿瘤抗生素的首次合成，同时对于制备拟药性结构（Ras 法尼基转移酶抑制剂文迪霉素的药效团）的类似物具有实用价值。
• Synthesis and NMR-Investigation of Annelated Pyrrole Derivatives
  作者：Helmut Spreitzer、Wolfgang Holzer、Christiane Puschmann、Andrea Pichler、Angelika Kogard、Klaus Tschetschkowitsch、Tatjana Heinze、Sabina Bauer、Nejati Shabaz

  DOI：10.3987/com-97-7877

  日期：——

  The synthesis of annelated pyrrole, namely isoindole derivatives by reaction of alpha,beta-unsaturated ketones, benzo- and naphthoquinone monoketals with tosylmethyl isocyanide is described. Moreover, detailed NMR spectroscopic studies (H-1, C-13) with the title compounds are presented.
• Total Synthesis of (±)-Nisamycin
  作者：Peter Wipf、Philip D. G. Coish

  DOI：10.1021/jo990413m

  日期：1999.7.1

  We have developed a highly convergent synthesis of the manumycin-type m-C7N-antibiotic nisamycin that is applicable to other members of this family of antibiotics. The synthesis features a three-step sequence to the epoxyquinol core that serves as a scaffold for the attachment of the polyene side chains. The eastern polyene side chain was constructed via a novel organozirconocene-mediated synthesis. Zirconocene methodology was also applied to the synthesis of the polyene side chains of asukamycin. The southern side chain of nisamycin was introduced via a Stille reaction that employed a vinyl bromo ketone, derived from an acid-sensitive bromo ketal. Pd-mediated coupling of the vinyl bromide with a stannyl TIPS ester gave TIPS-protected nisamycin that was readily converted to the natural product.