(8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl dimethylcarbamate | 1309752-00-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: (8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl dimethylcarbamate
• 英文别名: [(8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,14,15,16-octahydro-6H-cyclopenta[a]phenanthren-3-yl] N,N-dimethylcarbamate
• CAS: 1309752-00-8
• 化学式: C₂₁H₂₇NO₃
• 分子量: 341.45
• InChiKey: NZGGFYYWYVSFIY-WIRSXHRWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl dimethylcarbamate 在 sodium tetrahydroborate 、 silver hexafluoroantimonate 、 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 copper diacetate 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 19.0h， 生成 butyl (E)-3-((8R,9S,13S,14S)-3,17-bis((dimethylcarbamoyl)oxy)-13-methyl-7,8,9,11,12,13,14,15-octahydro-6H-cyclopenta[a]phenanthren-16-yl)acrylate
  参考文献：
  名称：

  Using Rh(III)-Catalyzed C–H Activation as a Tool for the Selective Functionalization of Ketone-Containing Molecules

  摘要：

  Due to the strong potential of C H activation in many areas of organic chemistry, the use of a pre-existing carbonyl group for the installation of a directing group to enable selective and predictable alpha-alkenylation with activated olefins as coupling partners is described. This Heck-type reaction would then lead either to beta,gamma-unsaturated ketones or to variously substituted 1,4-butadienes depending on the conditions used for the cleavage of the directing group.

  DOI：

  10.1021/ol500258q
• 作为产物：
  描述：

  雌酚酮 、 二甲氨基甲酰氯 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 2.0h， 生成 (8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl dimethylcarbamate
  参考文献：
  名称：

  Room-temperature Pd-catalyzed C–H chlorination by weak coordination: one-pot synthesis of 2-chlorophenols with excellent regioselectivity

  摘要：

  已开发出一种室温下Pd(II)催化的区域选择性氯化反应，可方便地用于广泛2-氯苯酚的一锅法合成。该反应在C-H氯化方面表现出出色的区域选择性和反应活性。这是在室温下温和C-H官能团化的罕见实例之一。

  DOI：

  10.1039/c3cc47431c

文献信息

• Mechanism-Driven Approach To Develop a Mild and Versatile C−H Amidation through Ir^IIICatalysis
  作者：Yeongyu Hwang、Yoonsu Park、Sukbok Chang

  DOI：10.1002/chem.201702397

  日期：2017.8.16

  catalysis. Reaction kinetics of a key C−N coupling step with acyl azide and 1,4,2‐dioxazol‐5‐one led us to conclude that dioxazolones are much more efficient in mediating the formation of a carbon−nitrogen bond from an iridacyclic intermediate. Computational analysis revealed that the origin of higher reactivity is asynchronous decarboxylation motion, which may facilitate the formation of Ir‐imido species

  本文描述了一种基于机制的方法，用于在Ir III催化下开发通用的CH酰胺化方案。关键的C-N偶联步骤与酰基叠氮化物和1,4,2-二恶唑5-1的反应动力学使我们得出结论，二恶唑酮在介导环环中间体形成碳氮键方面更为有效。计算分析表明，较高反应性的起源是异步脱羧运动，这可能促进Ir-酰亚胺基物种的形成。重要的是，化学计量反应性已成功转化为多种底物（18种不同类型）的催化活性，其中许多底物被认为对功能化具有挑战性。新方法的应用可以实现药物分子的后期功能化。
• Rhodium-Catalyzed Selective C–H Activation/Olefination of Phenol Carbamates
  作者：Tian-Jun Gong、Bin Xiao、Zhao-Jing Liu、Jian Wan、Jun Xu、Dong-Fen Luo、Yao Fu、Lei Liu

  DOI：10.1021/ol201140q

  日期：2011.6.17

  Rh(III)-catalyzed ortho C-H activation/olefination of phenol carbamates has been developed. High regioselectivity is observed with a range of phenol carbamates enabling efficient coupling with acrylates and styrenes. This reaction exhibits different reactivity as compared to the Pd-catalyzed ortho-arylation reaction of phenol esters and provides a new approach for the synthesis of ortho-substituted phenols.
• Carbamates: A Directing Group for Selective C–H Amidation and Alkylation under Cp*Co(III) Catalysis
  作者：Sourav Sekhar Bera、Modhu Sudan Maji

  DOI：10.1021/acs.orglett.0c00589

  日期：2020.4.3

  The selective reactivity of carbamate and thiocarbamate toward alkylation and amidation is reported under stable, high-valent, cost-effective cobalt(III) catalysis. This method reveals the wide possibility of designing a different branch of synthetically challenging yet highly promising asymmetric catalysts based on BINOL and SPINOL scaffolds. Late-stage C-H functionalization of L-tyrosine and estrone was also achieved through this approach. The mechanistic study shows that a base-assisted internal electrophilic substitution mechanism is operative here.
• Copper-Catalyzed Meta-Selective Arylation of Phenol Derivatives: An Easy Access to <i>m</i>-Aryl Phenols
  作者：Manikantha Maraswami、Hajime Hirao、Teck-Peng Loh

  DOI：10.1021/acscatal.0c05481

  日期：2021.2.19