(25R)-3β-acetoxyspirost-5-en-23-one | 28404-69-5

• 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: (25R)-3β-acetoxyspirost-5-en-23-one
• 英文别名: (25R)-3β-acetoxyspiros-5-en-23-one；(25R)-3b-acetoxyspirost-5-en-23-one；23-oxo-diosgenin acetate；23-oxodiosgenin acetate；23-ketodiosgenin acetate；(25r)-3beta-Acetoxyspirost-5-en-23-one；[(1S,2S,4S,5'R,6S,7S,8R,9S,12S,13R,16S)-5',7,9,13-tetramethyl-3'-oxospiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icos-18-ene-6,2'-oxane]-16-yl] acetate
• CAS: 28404-69-5
• 化学式: C₂₉H₄₂O₅
• 分子量: 470.649
• InChiKey: PWLXSTCKBUDQDW-QEIMIMDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (25R)-3β-acetoxyspirost-5-en-23-one 在 咪唑 、 sodium tetrahydroborate 、 sodium hydride 、 对甲苯磺酸 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 22.33h， 生成 薯蓣皂素乙酸盐
  参考文献：
  名称：

  Photoinduced Isomerization of 23-Oxosapogenins: Conformational Analysis and Spectroscopic Characterization of 22-Isosapogenins

  摘要：

  The first synthesis of 22-isospirostane derivatives is described. They were obtained by photochemical isomerization of 23-oxosapogenins. The structure of 23-oxo-22-isotigogenin acetate (12) was proved by a single crystal X-ray diffraction, while structures of 23-oxo-22-isodiosgenin acetate (13) and 23-oxo-22-isosarsasapogenin acetate (14) were elucidated by spectroscopic methods. 22-Isodiosgenin acetate (17) was obtained by NaBH4 reduction of the 23-oxo derivative 13 followed by the two-step Barton-McCombie deoxygenation procedure. Conformational analysis of 22-iso compounds was carried out with CD and NMR, as well as DFT calculations.

  DOI：

  10.1021/jo3022549
• 作为产物：
  描述：

  薯蓣皂素乙酸盐 在 三氟化硼乙醚 、 sodium carbonate 、 溶剂黄146 、 sodium nitrite 作用下， 反应 1.0h， 以35%的产率得到(25R)-3β-acetoxyspirost-5-en-23-one
  参考文献：
  名称：

  带有5α-羟基-6-氧代部分的二降胆固醇内酯的合成及其促进植物生长的活性。

  摘要：

  从易于获得的类固醇皂原素薯os皂苷元开始合成天然的二去胆甾内酯维斯汀和其他两个带有5α-羟基-6-氧代部分的非天然衍生物。获得的化合物在豆的第二节间伸长试验中显示出促进植物生长的活性。

  DOI：

  10.1016/j.jsbmb.2012.10.007

文献信息

• The Crystal Structure of Diosgenin Acetate and Its 23-Oxygenated Derivatives
  作者：Anielka Rosado-Abon、Nuria Esturau-Escofet、Marcos Flores-Álamo、Rafael Moreno-Esparza、Martín A. Iglesias-Arteaga

  DOI：10.1007/s10870-013-0404-3

  日期：2013.4

  The crystal structures of diosgenin acetate (1), 23-ketodiosgenin acetate (2), (23R)-23-hydroxydiosgenin 3-monoacetate (3) and (23S)-23-hydroxydiosgenin 3-monoacetate (4) are described. Compounds 1, 2 and 3 crystallized as a monoclinic system with a space group P21; while compound 4, crystallized as orthorhombic systems with space group P212121. The effects of the side chain modifications on the puckering parameters are presented and discussed. The crystal structures and NMR characterization of diosgenin acetate and its three 23-oxigenated derivatives are described.

  薯蓣皂苷元乙酸酯（1）、23-酮薯蓣皂苷元乙酸酯（2）、（23R）-23-羟基薯蓣皂苷元3-单乙酸酯（3）及（23S）-23-羟基薯蓣皂苷元3-单乙酸酯（4）的晶体结构被描述。化合物1、2和3结晶为单斜晶系，空间群P21；而化合物4结晶为正交晶系，空间群P212121。侧链修饰对折叠参数的影响被呈现和讨论。薯蓣皂苷元乙酸酯及其三个23-氧合衍生物的晶体结构和NMR表征被描述。
• Diacetoxyiodobenzene-mediated synthesis of unnatural furospirostane sapogenins derived from diosgenin and tigogenin
  作者：Jacqueline Sánchez-Flores、Margarita Romero-Ávila、Anielka Rosado-Abón、Marcos Flores-Álamo、Martín A. Iglesias-Arteaga

  DOI：10.1016/j.steroids.2013.05.013

  日期：2013.9

  Two unnatural steroid sapogenins bearing a furospirostane side chain were prepared starting from the readily available spirostane sapogenins, tigogenin and diosgenin following a synthetic protocol that included: (i) introduction of a carbonyl group at position C-23, (ii) diacetoxyiodobenzene-induced F-ring contraction and (iii) LiAlH4 reduction of the newly emerged methoxycarbonyl moiety. The structures

  两种带有呋喃螺甾烷侧链的非天然类固醇皂甙是从容易获得的螺甾烷皂甙元、tigogenin 和薯蓣皂甙元开始制备的，合成方案包括：（i）在 C-23 位引入羰基，（ii）二乙酰氧基碘苯诱导的 F -环收缩和 (iii) LiAlH4 还原新出现的甲氧基羰基部分。新化合物的结构由核磁共振和 X 射线研究证实。
• Mechanistic insights and new products of the reaction of steroid sapogenins with NaNO2 and BF3·Et2O in acetic acid
  作者：Yliana López、Karen M. Ruíz-Pérez、Rebeca Yépez、Rosa Santillan、Marcos Flores-Alamo、Martín A. Iglesias-Arteaga

  DOI：10.1016/j.steroids.2008.02.003

  日期：2008.7

  A detailed analysis of the course of the reaction of steroid sapogenins with NaNO(2) and BF(3).Et(2)O in acetic acid is presented and some evidences on the involved mechanism are provided. Two new products of the studied reaction were isolated and unambiguously characterized with the aid of NMR and single crystal X-ray diffraction.

  详细分析了类固醇皂甙元与NaNO（2）和BF（3）.Et（2）O在乙酸中的反应过程，并提供了有关其参与机理的一些证据。分离了所研究反应的两种新产物，并借助NMR和单晶X射线衍射对其进行了明确的表征。
• Stereospecific Synthesis of 1,6-Dioxadecalins and 2,2‘-Linked Ditetrahydrofurans by Rearrangement of Steroidal Spiroacetals
  作者：Carmen Betancor、Rosa L. Dorta、Raimundo Freire、Angeles Martín、Thierry Prangé、Ernesto Suárez

  DOI：10.1021/jo980834o

  日期：1998.9.1

  reduction of steroidal spiroacetal methanesulfonate derivatives, containing the 1,6-dioxaspiro[4.5]decan-10-yl ring system, with DIBALH promotes a new rearrangement to give steroidal 1,6-dioxadecalin (octahydropyrano[3,2-b]pyran) or 2,2'-linked ditetrahydrofuran (octahydro[2,2']bifuranyl) derivatives. To study the scope and selectivity of the reaction, several steroidal spiroacetals such as (23R,25R)

  用DIBALH还原包含1,6-dioxaspiro [4.5] decan-10-yl环系统的甾体螺缩醛甲磺酸衍生物，可促进新的重排，从而得到甾体1,6-二氧杂ade环素（八氢吡喃并[3,2-b]吡喃）或2,2'-连接的二四氢呋喃（八氢[2,2']双呋喃基）衍生物。为了研究反应的范围和选择性，使用了几种甾体螺缩醛，例如（23R，25R）-3beta-甲氧基-5alpha-spirostan-23-甲磺酸盐（2）及其23S-异构体（5）和（22R，23R，已经合成了甲磺酸25R）-3β-乙酰氧基-16β，23：23,26-二乙氧基胆甾-5-en-22-基（15）及其22S-异构体（19）。以绝对的区域和立体选择性重排化合物2，得到（22S，23S，25R）-3β-甲氧基-16β，23：22,26-二环氧-5α-胆甾烷（3），其具有顺式稠合的1,6- dioxadecalin环系统。化合物5的
• Abnormal Beckmann rearrangement in 23-hydroxyiminodiosgenin acetate
  作者：Martı́n A. Iglesias-Arteaga、Jesús Sandoval-Ramı́rez、Marian Y. Mata-Esma、Omar Viñas-Bravo、Sylvain Bernès

  DOI：10.1016/j.tetlet.2004.04.119

  日期：2004.6

  A new transformation of the spiroketal side chain of diosgenin is reported: treatment of 23-hydroxyiminodiosgenin acetate with phosphorous oxychloride in pyridine produced an abnormal Beckmann rearrangement directing to the cleavage of the spiroketal side chain and generating 23,24-bisnorchol-5-enic skeletons: (2′R)-3′-cyano-2′-methylpropyl 3β-acetoxy-16α-chloro-23,24-bisnorchol-5-en-22-oate as the

  据报道，薯in皂甙元的螺环侧链发生了新的转变：用吡啶中的三氯氧磷处理乙酸23-羟基亚氨基二s皂苷元乙酸酯产生异常的贝克曼重排，直接导致螺环侧链的断裂并产生23,24-双降冰片五烯骨架：（2' - [R）-3'-氰基-2'-甲基丙基3β乙酰氧基16α氯23,24-bisnorchol -5-烯-22 -酸酯作为主要产物，和少量的（2' - [R）-3'-氰基-2'-甲基丙基3β-乙酰氧基-16β-羟基-23,24-双降冰片烯5-en-22-酸酯和vespertilin乙酸酯。