3β-(toluene-4-sulfonyloxy)-5α-cholestane | 3381-52-0

• 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: 3β-(toluene-4-sulfonyloxy)-5α-cholestane
• 英文别名: 3β-hydroxy-5α-cholestane tosylate；3Beta-tosyloxy-5alpha-cholestane；[(3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl] 4-methylbenzenesulfonate
• CAS: 3381-52-0
• 化学式: C₃₄H₅₄O₃S
• 分子量: 542.867
• InChiKey: IAEKFZXJTDNGTI-JYFMWEQCSA-N

物化性质

• 熔点：
  136 °C
• 沸点：
  610.0±24.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.4
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3β-(toluene-4-sulfonyloxy)-5α-cholestane 在 sodium ethanolate 作用下， 生成 5α（H）-Cholestan-3α醇
  参考文献：
  名称：

  雷尼镍对单脂质的脱硫产品。

  摘要：

  DOI：

  10.1021/jo01014a047
• 作为产物：
  描述：

  4-甲苯磺酰氰 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 3β-(toluene-4-sulfonyloxy)-5α-cholestane
  参考文献：
  名称：

  O-Sulfinylation of alcohols with methanesulfonyl cyanide or p-toluenesulfonyl cyanide.

  摘要：

  Reaction of p-toluenesulfonyl cyanide or methanesulfonyl cyanide with alcohols in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,4-diazabicyclo[2.2.2]octane (DABCO) gives sulfinates in good yield. A mechanistic scheme involving sulfinyl cyanates 9 and 21 is suggested.

  DOI：

  10.1016/s0040-4020(01)96204-0

文献信息

• Site-Selective Thiolation of (Multi)halogenated Heteroarenes
  作者：Frederik Sandfort、Tobias Knecht、Tobias Pinkert、Constantin G. Daniliuc、Frank Glorius

  DOI：10.1021/jacs.0c01630

  日期：2020.4.15

  complementing established methodologies such as nucleophilic aromatic substitution or palladium-catalyzed coupling reactions. Experimental and computational studies suggest a radical chain mechanism with the key step being a homolytic aromatic substitution of the heteroaryl halide by an electrophilic thiyl radical, highlighting an underdeveloped reactivity mode of these radicals.

  报告了各种药物相关的富电子杂芳烃与硫醇的位点选择性硫醇化的一般和简单策略。这种温和而可靠的光催化协议能够在（多）卤化底物的最富电子位置进行 CS 耦合，补充已建立的方法，如亲核芳香取代或钯催化的耦合反应。实验和计算研究表明了一种自由基链机制，其关键步骤是杂芳基卤化物被亲电硫基自由基的均裂芳族取代，突出了这些自由基的不发达反应模式。
• Tris(3,6-dioxaheptyl)amine: A superior complexing agent for dissolving metal reactions
  作者：Ajay K. Bose、Pietro Mangiaracina

  DOI：10.1016/s0040-4039(00)95452-2

  日期：1987.1

  Commercially available tris(3,6-dioxaheptyl)amine (TDA-1) is an effective phase transfer catalyst for reactions with sodium-potassium alloy in tetrahydrofuran. Deoxygenation of acetates, dehalogenation, and hydrolysis of tosylates and mesylates proceed in high yield. The use of a deuterated alcohol during deoxygenation reactions leads to site-specific deuteration.

  市售的三（3,6-二氧杂庚基）胺（TDA-1）是一种有效的相转移催化剂，可与钠-钾合金在四氢呋喃中反应。乙酸酯的脱氧，脱卤代以及甲苯磺酸酯和甲磺酸酯的水解以高收率进行。在脱氧反应中使用氘代酒精会导致特定位置的氘代。
• Modification in the side chain of solomonsterol A: discovery of cholestan disulfate as a potent pregnane-X-receptor agonist
  作者：Valentina Sepe、Raffaella Ummarino、Maria Valeria D'Auria、Gianluigi Lauro、Giuseppe Bifulco、Claudio D'Amore、Barbara Renga、Stefano Fiorucci、Angela Zampella

  DOI：10.1039/c2ob25800e

  日期：——

  Seven synthetic analogues of the PXR (pregnane-X-receptor) potent natural agonist solomonsterol A were prepared by total synthesis. Their activity toward PXR was assessed by transactivation and RT-PCR assays. The study discloses cholestan disulfate (8) as a new, simplified agonist of PXR. By in vitro studies on hepatic cells we have demonstrated that this compound is a potent PXR agonist and functional characterization in human macrophages and hepatic stellate cells provided evidence that cholestan disulfate (8) has the ability to modulate the immune response triggered by bacterial endotoxin as well as to counter-activate hepatic stellate cell activation induced by thrombin. Because inhibition of immune-driven circuits might have relevance in the treatment of inflammation and liver fibrosis, the present data support the development of cholestan disulfate (8) in preclinical models of inflammatory diseases.

  通过全合成制备了七种孕烃X受体（PXR）强效天然激动剂solomonsterol A的合成类似物。通过转录激活和RT-PCR检测评估了它们对PXR的活性。研究表明，胆甾烷二硫酸盐（8）是一种新的、简化的PXR激动剂。通过对肝细胞的体外研究表明，该化合物是一种强效的PXR激动剂，并且在人巨噬细胞和肝星状细胞中的功能特性表明，胆甾烷二硫酸盐（8）具有调节细菌内毒素引发的免疫反应的能力，同时能反向激活凝血酶诱导的肝星状细胞激活。由于抑制免疫驱动通路可能对治疗炎症和肝纤维化具有相关性，当前数据支持在炎症性疾病的临床前模型中开发胆甾烷二硫酸盐（8）。
• Steroidal sulphur compounds. Part II. Pyrolysis, absolute configuration, and optical rotatory dispersion of steroidal methyl sulphoxides
  作者：D. Neville Jones、M. J. Green、M. A. Saeed、R. D. Whitehouse

  DOI：10.1039/j39680001362

  日期：——

  sulphur in 3β-acetoxy-(R)- and (S)-5α-methylsulphinylcholestane was also determined by an interpretation of intramolecular reactions involving the sulphoxide group. Two Cotton effects of opposite sign near 210 and 230 mµ occur in the o.r.d. spectra of the sulphoxides. Their relevance to chirality at sulphur and to restricted rotation about a C–S bond is discussed.

  在手性硫（[R ）-和（小号）-4β甲基亚磺酰基5α-胆甾烷，（- [R ）-和（小号）-5α-methylsulphinylcholestane，和3β乙酰氧基- （[R ） -和（小号）-5α-甲基亚磺酰基胆甾烷已通过热解法测定。碱催化的4β-亚砜氧化物差向异构化生成（R）-和（S）-4α-甲基亚磺酰基-5α-胆甾烷。还通过解释涉及亚砜基团的分子内反应来确定3β-乙酰氧基-（R）-和（S）-5α-甲基亚磺酰基胆甾烷中硫的手性。210和230 m µ附近的两个相反符号的棉花效应发生在亚砜的奥德谱中。讨论了它们与硫的手性和与C–S键的受限旋转的相关性。
• Stereospecific Nickel-Catalyzed Reductive Cross-Coupling of Alkyl Tosylate and Allyl Alcohol Electrophiles
  作者：Quentin D. Tercenio、Erik J. Alexanian

  DOI：10.1021/acs.orglett.1c02616

  日期：2021.9.17

  The stereospecific cross-coupling of easily accessed electrophiles holds significant promise in the construction of C–C bonds. Herein, we report a nickel-catalyzed reductive coupling of allyl alcohols with chiral, nonracemic alkyl tosylates. This cross-coupling delivers valuable allylation products with high levels of stereospecificity across a range of substrates. The catalytic system consists of

  易于获得的亲电子试剂的立体定向交叉偶联在 C-C 键的构建中具有重要的前景。在此，我们报道了烯丙醇与手性非外消旋烷基甲苯磺酸盐的镍催化还原偶联。这种交叉偶联可在一系列底物上提供具有高立体特异性的有价值的烯丙基化产物。该催化系统由简单的镍盐和市售的还原剂组成，重要的是代表了涉及两个亲电试剂的 C-O 键的交叉偶联的罕见例子。

表征谱图