1,6,6-trimethyl-10,11-dioxo-6,7,8,9,10,11-hexahydrophenanthro[1,2-b]furan-9-yl propionate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1,6,6-trimethyl-10,11-dioxo-6,7,8,9,10,11-hexahydrophenanthro[1,2-b]furan-9-yl propionate
• 英文别名: (1,6,6-trimethyl-10,11-dioxo-8,9-dihydro-7H-naphtho[1,2-g][1]benzofuran-9-yl) propanoate
• 化学式: C₂₂H₂₂O₅
• 分子量: 366.414
• InChiKey: ZIEDCOLEYKLAQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  73.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,6,6-trimethyl-10,11-dioxo-6,7,8,9,10,11-hexahydrophenanthro[1,2-b]furan-9-yl propionate 在 Selectfluor 作用下， 以 水 、 乙腈 为溶剂， 反应 12.0h， 以55%的产率得到7,7-difluoro-6,6-dihydroxy-1,1-dimethyl-5,8-dioxo-1,2,3,4,5,6,7,8-octahydrophenanthren-4-yl propionate
  参考文献：
  名称：

  呋喃萘醌的二氟化

  摘要：

  基于天然产物丹参酮及其类似物的呋喃萘醌骨架，开发了前所未有的二氟化反应。通过使用Selectfluor作为氟化源和H 2 O作为羟基源，获得了多种独特的多环α，α-二氟β，β-二羟基对苯醌产物，收率高达90％。机理研究表明，该反应可能会经历多个亲电和亲核取代，以及C–O和C–C键的断裂。该方法不仅为合成α，α-二氟酮提供了一种新方法，而且为生物学活性筛选提供了一系列独特的化学型。

  DOI：

  10.1021/acs.joc.7b01064
• 作为产物：
  描述：

  丹参酮 IIA 、 丙酸 在 2,2,6,6-四甲基哌啶氧化物 作用下， 以 氯苯 为溶剂， 反应 24.0h， 以91%的产率得到1,6,6-trimethyl-10,11-dioxo-6,7,8,9,10,11-hexahydrophenanthro[1,2-b]furan-9-yl propionate
  参考文献：
  名称：

  Catalyst-Free sp³ C–H Acyloxylation: Regioselective Synthesis of 1-Acyloxy Derivatives of the Natural Product Tanshinone IIA

  摘要：

  Tanshinone IIA is a valuable bioactive natural product isolated from the well-known Chinese herb Danshen. Structural manipulation of the A-ring of tanshinone IIA is rather limited. In this study, a substrate tautomerization-induced catalyst-free benzylic sp(3) C-H acyloxylation approach is reported that allows the direct introduction of various acyloxy groups at the A-ring benzylic methylene of various tanshinone IIA substrates, thus avoiding the use of expensive transition metal catalysts and the production of harmful byproducts. This approach features a unique acid-induced reversible enolization/oxa-conjugate addition process followed by oxidation to exclusively give a series of diverse 1-acyloxylated derivatives under simple conditions in a regioselective manner. Compared with the literature procedures, this protocol demonstrates a higher efficiency, a more robust functional-group tolerance, atom economy, and lower cost.

  DOI：

  10.1021/acs.jnatprod.6b00370

文献信息

• 二氟二羟基萘二酮类化合物、制备方法和应用
  申请人：中国科学院上海药物研究所

  公开号：CN109020799B

  公开（公告）日：2021-08-10

  本发明涉及一类2,2‑二氟‑3,3‑二羟基‑2,3‑二氢化萘‑1,4‑二酮类化合物、其制备方法和应用。其制备方法条件温和、简便易操作，适用于大量合成。其可以用于制抗肿瘤药物。
• Catalyst-Free sp³ C–H Acyloxylation: Regioselective Synthesis of 1-Acyloxy Derivatives of the Natural Product Tanshinone IIA
  作者：Chunyong Ding、Jie Li、Mingkun Jiao、Ao Zhang

  DOI：10.1021/acs.jnatprod.6b00370

  日期：2016.10.28

  Tanshinone IIA is a valuable bioactive natural product isolated from the well-known Chinese herb Danshen. Structural manipulation of the A-ring of tanshinone IIA is rather limited. In this study, a substrate tautomerization-induced catalyst-free benzylic sp(3) C-H acyloxylation approach is reported that allows the direct introduction of various acyloxy groups at the A-ring benzylic methylene of various tanshinone IIA substrates, thus avoiding the use of expensive transition metal catalysts and the production of harmful byproducts. This approach features a unique acid-induced reversible enolization/oxa-conjugate addition process followed by oxidation to exclusively give a series of diverse 1-acyloxylated derivatives under simple conditions in a regioselective manner. Compared with the literature procedures, this protocol demonstrates a higher efficiency, a more robust functional-group tolerance, atom economy, and lower cost.
• Difluorination of Furonaphthoquinones
  作者：Jie Li、Yu Xue、Zhoulong Fan、Chunyong Ding、Ao Zhang

  DOI：10.1021/acs.joc.7b01064

  日期：2017.7.21

  a wide range of unique polycyclic α,α-difluoro β,β-dihydroxyl para-quinone products were achieved with yields up to 90%. The mechanistic studies revealed that the reaction might undergo tandem multiple electrophilic and nucleophilic substitutions, as well as cleavages of C–O and C–C bonds. This approach not only provides a new method to synthesis of α,α-difluoro ketones, but also affords a series

  基于天然产物丹参酮及其类似物的呋喃萘醌骨架，开发了前所未有的二氟化反应。通过使用Selectfluor作为氟化源和H 2 O作为羟基源，获得了多种独特的多环α，α-二氟β，β-二羟基对苯醌产物，收率高达90％。机理研究表明，该反应可能会经历多个亲电和亲核取代，以及C–O和C–C键的断裂。该方法不仅为合成α，α-二氟酮提供了一种新方法，而且为生物学活性筛选提供了一系列独特的化学型。