(22R,23R,24R)-2α,3α,22,23-tetrahydroxy-5α-ergostan-6-one 2,3:22,23-diacetonide

• 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: (22R,23R,24R)-2α,3α,22,23-tetrahydroxy-5α-ergostan-6-one 2,3:22,23-diacetonide
• 英文别名: (22R,23R,24R)-2α,3α:22,23-di(isopropylidenedioxy)-24-methyl-5α-cholestan-6-one；24-epicastasterone diacetonide；(1S,2R,4R,8S,10S,13S,14S,17R,18S)-17-[(1S)-1-[(4R,5R)-2,2-dimethyl-5-[(2R)-3-methylbutan-2-yl]-1,3-dioxolan-4-yl]ethyl]-2,6,6,18-tetramethyl-5,7-dioxapentacyclo[11.7.0.02,10.04,8.014,18]icosan-11-one
• 化学式: C₃₄H₅₆O₅
• 分子量: 544.816
• InChiKey: HIPXZCRJNSEFNG-UPIFBQNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  39
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.97
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (22R,23R,24R)-2α,3α,22,23-tetrahydroxy-5α-ergostan-6-one 2,3:22,23-diacetonide 在 吡啶 、 ammonium cerium (IV) nitrate 、 二甲基二环氧乙烷 作用下， 以 二氯甲烷 、 水 、 丙酮 、 乙腈 、 苯 为溶剂， 反应 5.0h， 生成 (22R,23R,24R)-3β-chloro-2α,3α-(carbonyldioxy)-22,23-(isopropylidenedioxy)-24-methyl-5α-cholestan-6-one
  参考文献：
  名称：

  A stereospecific pathway for the introduction of deuterium on the brassinosteroid skeleton by reductive dechlorination of chlorocarbonates

  摘要：

  A new and efficient procedure for the preparation of brassinosteroids labeled with hydrogen isotopes was developed. A four-step reaction sequence started with the selective oxidation of a 2,3-diol group to an alpha-hydroxy ketone, which was converted stereospecifically into a chlorocarbonate by reaction with triphosgene. A subsequent Pd-catalyzed reductive dechlorination with deuterium gas yielded deuterium-labeled brassinosteroid 2,3-carbonates. The reaction sequence was completed by base-catalyzed hydrolysis of the cyclic carbonate. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.02.013
• 作为产物：
  描述：

  (2R,3S,5S,8R,9R,10R,13S,14S,17R)-17-[(2S,3R,4R,5R)-3,4-二羟基-5,6-二甲基庚烷-2-基]-2,3-二羟基-10,13-二甲基-1,2,3,4,5,7,8,9,11,12,14,15,16,17-十四氢环戊烯并[a]菲-6-酮 、 2,2-二甲氧基丙烷 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 以96%的产率得到(22R,23R,24R)-2α,3α,22,23-tetrahydroxy-5α-ergostan-6-one 2,3:22,23-diacetonide
  参考文献：
  名称：

  Preparation and synthetic application of partially protected brassinosteroids

  摘要：

  Preparation of partially protected brassinosteroids is achieved through the reaction of the source material (24-epicastasterone and 24-epibrassinolide) with diol-specific reagents (2,2-dimethoxypropane and methylboronic acid). The obtained products were shown to be useful synthetic intermediates for further preparation of minor representatives of this class of natural phytohormones (such as 3 24, diepicastasterone and 3-dehydro-24-epibrassinolide). (C) 2009 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2009.09.010

文献信息

• Synthesis of 2,24-Diepicastasterone and 3,24-Diepicastasterone as Potential Brassinosteroid Metabolites of the Cockroach Periplaneta americana
  作者：Brunhilde Voigt、Andrea Porzel、Günter Adam、Dieter Golsch、Waldemar Adam、Christoph Wagner、Kurt Merzweiler

  DOI：10.1135/cccc20020091

  日期：——

  Investigations of the metabolic conversion of the phytohormone 24-epicastasterone (1) in the cockroach Periplaneta americana (L.) required the synthesis of 2,24-diepicastasterone (4), 3,24-diepicastasterone (7b) and 2-dehydro-3,24-diepicastasterone (9) as reference standards. 2,24-Diepicastasterone (4) was synthesized from 2α,3α-epoxy derivative 2 as well as from the 2β,3β-epoxy-22,23-diol 3 by acid-catalyzed water addition to the epoxy function leading to the desired 2β,3α-trans functionality. 3,24-Diepicastasterone (7b) was prepared by NaBH₄-reduction of the 3-oxo derivative 6. Upon deprotection conditions from the ketol acetonides 6 and 8 in both cases 2-dehydro-3,24-diepicastasterone (9) was obtained. The structure of 2,24-diepicastasterone (4) was confirmed by X-ray analysis.

  对植物激素24-epicastasterone (1)在美洲蠊（Periplaneta americana (L.)）中的代谢转化的研究需要合成2,24-diepicastasterone (4)、3,24-diepicastasterone (7b)和2-dehydro-3,24-diepicastasterone (9)作为参考标准。2,24-diepicastasterone (4)由2α,3α-环氧衍生物2和2β,3β-环氧-22,23-二醇3经酸催化加水反应制得，得到所需的2β,3α-trans官能团。3,24-diepicastasterone (7b)通过NaBH₄还原3-酮衍生物6制备而成。在去保护酮醇丙酮酸酯6和8的条件下，两种情况都得到2-dehydro-3,24-diepicastasterone (9)。2,24-diepicastasterone (4)的结构经过X射线分析得到证实。
• Preparation and synthetic application of partially protected brassinosteroids
  作者：Vladimir A. Khripach、Vladimir N. Zhabinskii、Yuliya Y. Zhiburtovich、Galina V. Ivanova、Olga V. Konstantinova、Dmitrii V. Tsavlovskii、Sybille Lorenz、Bernd Schneider

  DOI：10.1016/j.steroids.2009.09.010

  日期：2010.1

  Preparation of partially protected brassinosteroids is achieved through the reaction of the source material (24-epicastasterone and 24-epibrassinolide) with diol-specific reagents (2,2-dimethoxypropane and methylboronic acid). The obtained products were shown to be useful synthetic intermediates for further preparation of minor representatives of this class of natural phytohormones (such as 3 24, diepicastasterone and 3-dehydro-24-epibrassinolide). (C) 2009 Elsevier Inc. All rights reserved.
• A stereospecific pathway for the introduction of deuterium on the brassinosteroid skeleton by reductive dechlorination of chlorocarbonates
  作者：Aleš Marek、Mahadeo R. Patil、Blanka Klepetářová、Ladislav Kohout、Tomáš Elbert

  DOI：10.1016/j.tetlet.2012.02.013

  日期：2012.4

  A new and efficient procedure for the preparation of brassinosteroids labeled with hydrogen isotopes was developed. A four-step reaction sequence started with the selective oxidation of a 2,3-diol group to an alpha-hydroxy ketone, which was converted stereospecifically into a chlorocarbonate by reaction with triphosgene. A subsequent Pd-catalyzed reductive dechlorination with deuterium gas yielded deuterium-labeled brassinosteroid 2,3-carbonates. The reaction sequence was completed by base-catalyzed hydrolysis of the cyclic carbonate. (C) 2012 Elsevier Ltd. All rights reserved.