17β-hydroxy-4,5-secoandrost-3-yn-5-one | 17541-44-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 17β-hydroxy-4,5-secoandrost-3-yn-5-one
• 英文别名: 5-Oxo-17β-hydroxy-4,5-seco-androstin-(3)；(3S,3aS,5aS,6R,9aS,9bS)-6-but-3-ynyl-3-hydroxy-3a,6-dimethyl-1,2,3,4,5,5a,8,9,9a,9b-decahydrocyclopenta[a]naphthalen-7-one
• CAS: 17541-44-5
• 化学式: C₁₉H₂₈O₂
• 分子量: 288.43
• InChiKey: WJFXUGBKJORMEV-NLQHDTCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  17β-hydroxy-4,5-secoandrost-3-yn-5-one 在 Lindlar's catalyst 吡啶 、 咪唑 、 喹啉 、 4-二甲氨基吡啶 、 盐酸羟胺 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 溶剂黄146 、 对甲苯磺酰氯 、 间氯过氧苯甲酸 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 氯仿 为溶剂， 65.0 ℃ 、101.33 kPa 条件下， 反应 65.0h， 生成 Benzoic acid (1S,3aS,3bS,8S,10aR,10bS,12aS)-10a,12a-dimethyl-6-oxo-8-(toluene-4-sulfonyloxy)-hexadecahydro-6a-aza-benzo[3,4]cyclohepta[1,2-e]inden-1-yl ester
  参考文献：
  名称：

  A novel stereospecific rearrangement of 3-substituted B-homo-5-azasteroids to their A-nor analogs. Preparation, stereochemistry, and conformational studies

  摘要：

  The novel 3-alpha- and 3-beta-hydroxy-B-homo-5-azasteroid lactams 4 and 5 were prepared from testosterone. When the hydroxyl group in these compounds is converted into a leaving group, rearrangement to the corresponding A-nor azasteroids occurs under a variety of conditions, along with competing substitution with inversion of configuration at C-3. The rearrangements proceed with complete stereospecificity and are faster and more efficient in the 3-alpha-series. The observed stereochemistry, as well as the results of molecular modeling, low-temperature NMR, and X-ray crystallographic studies support a mechanism involving neighboring-group participation by the nitrogen atom in the departure of the nucleofuge from C-3 via the formation of aziridinium ion intermediates. Compounds in the 3-alpha-series require prior ring-flipping to the A-boat conformation, while those in the 3-beta-series react through the corresponding A-chairs. The differences in the free energies of the A-boat and A-chair forms are greater in the 3-beta-compounds (1.6-3.4 kcal/mol) than in the corresponding 3-alpha-isomers (0.1-1.3 kcal/mol). The 3-alpha-chloro derivative 19 exists mainly as the A-chair in solution (DELTA-G = 0.3 kcal/mole; DELTA-G* = 12.2 kcal/mol), but crystallizes in the A-boat conformation. Molecular modeling studies of several 3-substituted derivatives and X-ray investigations of 19 and its 3-beta-isomer 20 also reveal separate flip forms of the B-rings associated with the A-chair and A-boat conformations in each case. Relief of steric hindrance between one of the hydrogen atoms at C-19 and the beta-hydrogen at C-7 (this H-H contact is only 1.98 angstrom in the crystal structure of 19) in the A-boat conformations of the 3-alpha-series enhances anchimeric assistance to the departure of the leaving group and facilitates the rearrangements of these compounds relative to their 3-beta-counterparts.

  DOI：

  10.1021/jo00041a013
• 作为产物：
  描述：

  4,5-环氧-17beta-羟基-5-雄甾烷-3-酮 在 对甲苯磺酰肼 作用下， 以 溶剂黄146 为溶剂， 以93%的产率得到17β-hydroxy-4,5-secoandrost-3-yn-5-one
  参考文献：
  名称：

  Intramolecular Wittig cyclization: a novel route to previously unknown 3-thia and 3-sulfinyl analogs of testosterone

  摘要：

  DOI：

  10.1021/jo00170a055
• 作为试剂：
  描述：

  4-甲基苯基亚硫酰氯 在 17β-hydroxy-4,5-secoandrost-3-yn-5-one 作用下， 以 吡啶 为溶剂， 反应 5.0h， 以22%的产率得到4-Methyl-benzenesulfinic acid (3S,3aS,5aS,6R,9aS,9bS)-6-but-3-ynyl-3a,6-dimethyl-7-oxo-dodecahydro-cyclopenta[a]naphthalen-3-yl ester
  参考文献：
  名称：

  Boar, Robin B.; Jones, Susan L.; Patel, Arvind C., Journal of the Chemical Society. Perkin transactions I, 1982, p. 513 - 516

  摘要：

  DOI：

文献信息

• Identification of a Fossil Sterane Biomarker in Crude Oil - an Androstane with a Modified Carbon Skeleton
  作者：Matthias Bender、Marc Schmidtmann、Jürgen Rullkötter、Roger E. Summons、Jens Christoffers

  DOI：10.1002/ejoc.201300788

  日期：2013.9

  of four stereoisomers of 3-methyl-A-nor-androstane (4 % overall yield) was prepared by ionic hydrogenation of the olefin after A-ring recyclization in three steps. 17-Methyl-18-nor-androstane was synthesized in four steps as a mixture of isomers (58 % overall yield) from dihydrotestosterone with a Wagner–Meerwein shift of the 13β-methyl group to C-17 as the key step. Pure 17β- and 17α-methyl-18-nor-13α-androstane

  制备了雄烷的三种结构异构体，用于与来自阿曼的地质样品中的三种未知的化石 C19H32 有机生物标志物（洗脱顺序为“19A”、“19B”和“19C”）进行比较。3β-甲基-A-去甲雄甾烷由睾酮分六步制备（总产率为8%）。该序列的关键步骤是 A 环的 Eschenmoser 断裂和再循环。3-甲基-A-去甲雄甾烷的四种立体异构体的混合物（4%总产率）是通过在三个步骤中的A环再环化之后的烯烃的离子氢化来制备的。17-Methyl-18-nor-androstane 是由二氢睾酮合成的异构体混合物（58% 的总产率），以 13β-甲基向 C-17 的 Wagner-Meerwein 转变为关键步骤，分四步合成。纯 17β- 和 17α-methyl-18-nor-13α-androstane（总产率为 4% 和 2%，分别）在 Wagner-Meerwein 重排产物的 α-氧化和随后的还原后的三
• Novel A-nor sterols: Synthesis and stereochemistry
  作者：S PRADHAN、V GIRIJAVALLABHAN

  DOI：10.1016/s0039-128x(69)80056-5

  日期：1969.1

  Abstract A new and simple method of synthesis of A-nor sterols having a tertiary hydroxyl group allylic to an exocyclic methylene is described consisting of utilization of the Eschenmoser Fragmentation of αβ -epoxy ketones and the Stork Ring-closure of acetylenic ketones. 4 β ,5 β -epoxycholestan-3-one gave 3-methylene-A-nor-cholestan-5 β -ol together with 3-methyl-A-nor-cholest-3-ene (III). The structure

  摘要 描述了一种合成具有叔羟基烯丙基到环外亚甲基的 A-nor 甾醇的新的简单方法，该方法包括利用 αβ-环氧酮的 Eschenmoser 断裂和炔酮的 Stork 闭环。4 β ,5 β-epoxycholestan-3-one 与 3-methyl-A-nor-cholest-3-ene (III) 一起生成 3-methylene-A-nor-cholestan-5 β-ol。前者的结构通过NMR、IR和烯丙基异构化确定。第 5 位的立体化学是通过与从 III 获得的二醇和次要环氧化物的相关性建立的，并且使用 NMR 数据为其指定构型。顺式-hydrindane 的排他性形成在 Stork 闭环中带来了意想不到的立体选择性。17 β-羟基雄甾烷类似物是通过吡喃醚制备的。
• A study of the Stork reductive cyclization of steroidal acetylenic ketones in aprotic media with the naphthalene anion radicals
  作者：Suresh K. Pradhan、Tarur V. Radhakrishnan、Raman Subramanian

  DOI：10.1021/jo00873a012

  日期：1976.5
• US3984474A
  申请人：——

  公开号：US3984474A

  公开（公告）日：1976-10-05