(22E)-6β-methoxy-3α,5-cyclo-24-α-methyl-5α-cholest-22-ene

• 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: (22E)-6β-methoxy-3α,5-cyclo-24-α-methyl-5α-cholest-22-ene
• 英文别名: (22E,24S)-6β-methoxy-24-methyl-3α,5-cyclo-5α-cholest-22-ene；(24S,E)-6β-methoxy-3α,5-cycloergostan-22-ene；(1S,2R,5R,7R,8R,10S,11S,14R,15R)-14-[(E,2R,5S)-5,6-dimethylhept-3-en-2-yl]-8-methoxy-2,15-dimethylpentacyclo[8.7.0.02,7.05,7.011,15]heptadecane
• 化学式: C₂₉H₄₈O
• 分子量: 412.7
• InChiKey: QSVAVMAXJNOUGW-DTESEBARSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (22E)-6β-methoxy-3α,5-cyclo-24-α-methyl-5α-cholest-22-ene 在 四氧化锇 、 dihydroquinidine 4-chlorobenzoate 、 甲基磺酰胺 、 水 、 potassium carbonate 、 对甲苯磺酸 、 potassium hexacyanoferrate(III) 作用下， 以 1,4-二氧六环 、 水 、 叔丁醇 为溶剂， 反应 364.0h， 生成 6-deoxoteasterone
  参考文献：
  名称：

  Takatsuto, Suguru; Watanabe, Tsuyoshi; Fujioka, Shozo, Journal of Chemical Research, Miniprint, 1997, # 4, p. 901 - 924

  摘要：

  DOI：
• 作为产物：
  描述：

  Toluene-4-sulfonic acid (E)-(3R,6R)-6-((1aR,3aR,3bS,5aR,6R,8aS,8bS,10R,10aR)-10-methoxy-3a,5a-dimethyl-hexadecahydro-cyclopenta[a]cyclopropa[2,3]cyclopenta[1,2-f]naphthalen-6-yl)-2,3-dimethyl-hept-4-enyl ester 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.75h， 以198 mg的产率得到(22E)-6β-methoxy-3α,5-cyclo-24-α-methyl-5α-cholest-22-ene
  参考文献：
  名称：

  24α-甲基类固醇合成中的 [3,3]-Claisen 重排

  摘要：

  本文阐述了一种以豆甾醇为原料合成新春甾醇和菜油甾醇的改进方法。所提出的方法基于 Delta23-22-烯丙醇的克莱森重排，具有 22-羟基的各种构型和 Delta23-双键的几何形状。它允许完全使用起始类固醇来制备 24α-甲基衍生物。可以部分控制 C-25 的立体化学。Delta22-双键的氢化随着C-24烷基取代基的部分异构化而进行。克莱森重排的爱尔兰酯烯醇化物变体被证明可用于制备含有 Delta22,25-系统的 24α-甲基类固醇。

  DOI：

  10.1016/s0039-128x(02)00007-7

文献信息

• Synthetic routes to campesterol and dihydrobrassicasterol: a first reported synthesis of the key phytosterol dihydrobrassicasterol
  作者：N.M. O'Connell、Y.C. O'Callaghan、N.M. O'Brien、A.R. Maguire、F.O. McCarthy

  DOI：10.1016/j.tet.2012.04.060

  日期：2012.6

  Phytosterols are increasingly used as health supplements in functional foods and are associated with having both positive and negative effects on health. Given this disparity, an investigation of their full individual biological profile is imperative in order to assure food safety. This paper describes the de novo synthesis of pure phytosterols in multigram scale and we report the first synthesis of

  植物甾醇越来越多地用作功能性食品中的健康补充剂，并且与对健康的正面和负面影响有关。考虑到这种差异，必须对其完整的个体生物学特性进行调查，以确保食品安全。本文以毫克级从头开始描述纯植物甾醇的从头合成，并且我们报告了关键植物甾醇二氢Brassicasterol的首次合成以及与菜油甾醇的路线比较。包括对化合物，混合物及其前体的13 C NMR光谱数据的完整分配，进行了详细的光谱分析，从而潜在地将NMR光谱用作分析这些固醇混合物的工具。
• Synthesis of Cathasterone and its Related Putative Intermediates in Brassinolide Biosynthesis†
  作者：Suguru Takatsuto、Hiroki Kuriyama、Takahiro Noguchi、Hiroyuki Suganuma、Shozo Fujioka、Akira Sakurai

  DOI：10.1039/a704788f

  日期：——

  The putative intermediates in brassinolide biosynthesis, 22α-hydroxycampesterol 1, 6-deoxocathasterone and its 6α-hydroxylated compound 3, as well as cathasterone 4, are synthesized from a known (22E,24S)-6β-methoxy-3α,5-cyclo-5α-ergost-22-ene 5.

  在芸苔素的生物合成，22推定的中间体α -hydroxycampesterol 1，6- deoxocathasterone及其6 α羟基化化合物3，以及cathasterone 4，是从公知的（22合成ê，24小号）-6 β -甲氧基-3- α，5-环5 α -ergost -22-烯5。
• Enantioselective catalytic approach to the C23–C28 subunit of 24α-methyl steroids
  作者：Viktoryia S. Yakimchyk、Volha V. Kazlova、Alaksiej L. Hurski、Rimma G. Savchenko、Svetlana A. Kostyleva、Vladimir N. Zhabinskii、Vladimir A. Khripach

  DOI：10.1016/j.steroids.2019.05.003

  日期：2019.8

  by the reaction between isovaleraldehyde and nitroethylene catalyzed by only 2% of (S)-trimethylsilyldiphenylprolinol. Removal of one "extra" carbon from the nitroalcohol was achieved by Ni-catalyzed hydrodecarboxylation of the redox-active ester intermediate. The synthesized C23-C28 fragment was attached to a steroidal core by Julia-Kocienski reaction of a steroidal aldehyde with metallated C23-C28

  据报道基于催化方法对映体选择性合成樟脑甾族化合物的C23-C28亚基。合成从（S）-2-异丙基-4-硝基丁-1-醇开始，其通过仅2％的（S）-三甲基甲硅烷基二苯基脯氨醇催化的异戊醛与硝基乙烯之间的反应容易获得。通过氧化还原活性酯中间体的Ni催化加氢脱羧，可以从硝基醇中除去一个“多余的”碳。通过类固醇醛与金属化的C23-C28砜的Julia-Kocienski反应，将合成的C23-C28片段连接至类固醇核心。所获得的烯烃化产物易于转化为菜油甾醇和（Z）-22-脱氢菜油甾醇的前体。
• A formal synthesis of brassinolide
  作者：T. Schmittberger、D. Uguen

  DOI：10.1016/s0040-4039(97)00474-7

  日期：1997.4

  Enzyme-catalysed differentiation of hydroxy groups in a C2v-shaped tetraol-sulfide, combined with a E-stereoconvergent Ramberg-Bäcklund process, allowed to prepare pure (2S)-2,3-dimethyl-1-iodobutane, which could be coupled with a 3,5-cyclopregnane-20-thiomethanol derivative so as to give an efficient precursor of the title vegetal hormone.

  酶催化的C 2v形四醇-硫化物中羟基的分化，结合E-立体收敛的Ramberg-Bäcklund工艺，可以制备纯净的（2 S）-2,3-二甲基-1-碘丁烷加上3,5-环戊烯-20-硫代甲醇衍生物，以提供标题植物激素的有效前体。
• Highly Stereocontrolled Formal Synthesis of Brassinolide via Chiral Sulfoxide-Directed S_N2‘ Reactions
  作者：Joseph P. Marino、Alfonso de Dios、Laura J. Anna、Roberto Fernández de la Pradilla

  DOI：10.1021/jo951264k

  日期：1996.1.1

  An efficient stereocontrolled methodology for the preparation of the four contiguous chiral centers of the brassinosteroid side chain is described. Allylic mesyloxy sulfinyl steroids have been found to undergo highly stereoselective S(N)2' displacements when treated with cyanocuprates that provide the required acyclic stereocontrol in the key C-24 position of the steroidal side chain. Preparation of a direct precursor of brassinolide]I, as well as a precursor of naturally occurring (24R)-epibrassinolide, (+)-18, is carried out in two additional steps utilizing asymmetric dihydroxylations of(22E)-olefins (+)-2 and (+)-17. In this manner, a formal synthesis of this plant growth promoter has been completed, and the extension of the scope of this methodology has been explored providing a straightforward route to this family of steroids. Alternative routes to the key olefin (+)-2 are also outlined. Improved selectivity in the addition to aldehyde 7 for the preparation of the Cram (22R)-allylic hydroxy sulfoxides is achieved by controlling the chirality at sulfur or by a condensation-symmetric oxidation sequence employing the analogous vinyl sulfide reagent 22.