cholesteryl 2-bromopropionate

• 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: cholesteryl 2-bromopropionate
• 英文别名: Cholesteryl-α-bromopropionate；(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl 2-bromopropanoate；[(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl] 2-bromopropanoate
• 化学式: C₃₀H₄₉BrO₂
• 分子量: 521.622
• InChiKey: HQCIIKWOMRRRPN-VAEUHUSKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.3
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  胆固醇	cholesterol	57-88-5	C27H46O	386.662

反应信息

• 作为反应物：
  描述：

  2-二苯基膦-联苯 、 cholesteryl 2-bromopropionate 在 2,2,6,6-四甲基-3,5-庚二酮 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 双氧水 、 potassium acetate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以81%的产率得到(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl 2-(2'-(diphenylphosphoryl)-[1,1'-biphenyl]-3-yl)propanoate
  参考文献：
  名称：

  协同配体促进的P （III） -Directed钌催化远程元叔膦的-C-H烷基化

  摘要：

  在本文中，我们公开了钌催化的元通过使用固有的P.膦-选择性C-H活化（III）作为定向基团。2,2,6,6-四甲基庚烷-3,5-二酮充当配体并在促进间位烷基化方面表现出出色的性能。该方案允许间位烷基化的叔膦的有效而直接的合成。评估了几种间位烷基化的膦在Pd催化的Suzuki偶联中的作用，发现其优于市售的邻位取代的膦。通过双官能化膦的合成进一步证明了该方法的实用性。

  DOI：

  10.1021/acs.orglett.1c00237
• 作为产物：
  描述：

  胆固醇 、 2-溴丙酰溴 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到cholesteryl 2-bromopropionate
  参考文献：
  名称：

  3-Alkyl-6-Chloro-2-pyrones:  Selective Inhibitors of Pancreatic Cholesterol Esterase

  摘要：

  A series of 3-alkyl-6-chloro-2-pyrones with cyclohexane rings tethered to the S-position was synthesized. The tether ranged from 0 to 4 methylene units. Inhibition of pancreatic-cholesterol esterase by this series of pyrones was markedly dependent upon the length of the tether. Dissociation constants as low as 25 nM were observed for 6-chloro-3-(1-ethyl-2-cyclohexyl)-2-pyranone. This class of cholesterol esterase inhibitors functioned as simple competitive inhibitors of substrate binding rather than as suicide substrates or active site inactivators. Trypsin and chymotrypsin were not strongly inhibited by this class of pyrones. Selectivities for cholesterol esterase were greater than 10(3). This is in contrast to 3-aryl-6-chloro-2-pyrones which are nonselective, irreversible inactivators of serine hydrolases, Thus, replacement of the 3-aryl group by an appropriately tethered 3-alkyl ring can produce highly selective inhibitors of cholesterol esterase. A second series of halogen-containing esters was prepared in which cholesterol was esterified with alpha-haloacyl halides. These haloesters were simple substrates of cholesterol esterase with no evidence of irreversible inactivation.

  DOI：

  10.1021/jm990309x

文献信息

• Recyclable Ruthenium Catalyst for Distal <i>meta</i> ‐C−H Activation
  作者：Isaac Choi、Valentin Müller、Yanhui Wang、Kai Xue、Rositha Kuniyil、Loren B. Andreas、Volker Karius、Johan G. Alauzun、Lutz Ackermann

  DOI：10.1002/chem.202003622

  日期：2020.11.26

  unprecedented hybrid‐ruthenium catalysis for distal meta‐C−H activation. The hybrid‐ruthenium catalyst was recyclable, as was proven by various heterogeneity tests, and fully characterized with various microscopic and spectroscopic techniques, highlighting the physical and chemical stability. Thereby, the hybrid‐ruthenium catalysis proved broadly applicable for meta‐C−H alkylations of among others purine‐based

  我们公开了前所未有的用于远端元-C-H激活的混合钌催化。各种非均质性测试证明，杂化钌催化剂是可回收的，并通过各种显微和光谱技术进行了充分表征，突出了物理和化学稳定性。因此，杂化钌催化被证明广泛适用于基于嘌呤的核苷和天然产物缀合物的间位-C-H烷基化。此外，通过可见光照射的元-C-H激活以及对位选择性C-H激活进一步反映了其多功能性。
• Anti‐Selective Carbosilylation: Nickel‐Catalyzed Multicomponent Reaction of Solid Me₃SiZnI
  作者：Revathi Chandrasekaran、Keerthika Selvam、Thayalan Rajeshkumar、Tamilselvi Chinnusamy、Laurent Maron、Ramesh Rasappan

  DOI：10.1002/anie.202318689

  日期：——

  vinylsilanes via the anti-selective addition of a novel solid Me3SiZnI to terminal alkynes. An equilibrium exists between the intermediate syn- and anti-adducts, where the anti-selectivity is determined by the larger barrier at the single electron reduction of alkyl halides and the thermodynamic stability of the Ni(III) adduct.

  这项研究提出了一种独特的方法，通过将新型固体 Me 3 SiZnI 反选择性加成到末端炔烃上，选择性合成立体定义的三取代乙烯基硅烷。中间顺式加合物和反式加合物之间存在平衡，其中反选择性由烷基卤化物单电子还原时的较大势垒和 Ni(III) 加合物的热力学稳定性决定。
• Yano; Nabata; Aoki, Molecular Crystals and Liquid Crystals (1969-1991), 1980, vol. 70, # 1-4, p. 163 - 168
  作者：Yano、Nabata、Aoki

  DOI：——

  日期：——
• 3-Alkyl-6-Chloro-2-pyrones:  Selective Inhibitors of Pancreatic Cholesterol Esterase
  作者：Lorraine M. Deck、Miranda L. Baca、Stephanie L. Salas、Lucy A. Hunsaker、David L. Vander Jagt

  DOI：10.1021/jm990309x

  日期：1999.10.1

  A series of 3-alkyl-6-chloro-2-pyrones with cyclohexane rings tethered to the S-position was synthesized. The tether ranged from 0 to 4 methylene units. Inhibition of pancreatic-cholesterol esterase by this series of pyrones was markedly dependent upon the length of the tether. Dissociation constants as low as 25 nM were observed for 6-chloro-3-(1-ethyl-2-cyclohexyl)-2-pyranone. This class of cholesterol esterase inhibitors functioned as simple competitive inhibitors of substrate binding rather than as suicide substrates or active site inactivators. Trypsin and chymotrypsin were not strongly inhibited by this class of pyrones. Selectivities for cholesterol esterase were greater than 10(3). This is in contrast to 3-aryl-6-chloro-2-pyrones which are nonselective, irreversible inactivators of serine hydrolases, Thus, replacement of the 3-aryl group by an appropriately tethered 3-alkyl ring can produce highly selective inhibitors of cholesterol esterase. A second series of halogen-containing esters was prepared in which cholesterol was esterified with alpha-haloacyl halides. These haloesters were simple substrates of cholesterol esterase with no evidence of irreversible inactivation.
• Cooperative Ligand-Promoted P^(III)-Directed Ruthenium-Catalyzed Remote <i>Meta</i>-C–H Alkylation of Tertiary Phosphines
  作者：Zheng-Xin Zhou、Jia-Wei Li、Liang-Neng Wang、Ming Li、Yue-Jin Liu、Ming-Hua Zeng

  DOI：10.1021/acs.orglett.1c00237

  日期：2021.3.19

  ruthenium-catalyzed meta-selective C–H activation of phosphines by using intrinsic P(III) as a directing group. 2,2,6,6-Tetramethylheptane-3,5-dione acts as the ligand and exhibits an excellent performance in boosting the meta-alkylation. The protocol allows an efficient and straightforward synthesis of meta-alkylated tertiary phosphines. Several meta-alkylated phosphines were evaluated for Pd-catalyzed Suzuki coupling

  在本文中，我们公开了钌催化的元通过使用固有的P.膦-选择性C-H活化（III）作为定向基团。2,2,6,6-四甲基庚烷-3,5-二酮充当配体并在促进间位烷基化方面表现出出色的性能。该方案允许间位烷基化的叔膦的有效而直接的合成。评估了几种间位烷基化的膦在Pd催化的Suzuki偶联中的作用，发现其优于市售的邻位取代的膦。通过双官能化膦的合成进一步证明了该方法的实用性。