rac-(6R^*)-2-methyl-6-[(4R^*,7aR^*)-7a-methyl-4-(phenylthio)octahydroinden-1-yl]heptan-2-ol

• 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: rac-(6R^*)-2-methyl-6-[(4R^*,7aR^*)-7a-methyl-4-(phenylthio)octahydroinden-1-yl]heptan-2-ol
• 英文别名: (6R)-6-[(1R,3aR,4R,7aR)-4-(benzenesulfonyl)-7a-methyl-1,2,3,3a,4,5,6,7-octahydroinden-1-yl]-2-methylheptan-2-ol
• 化学式: C₂₄H₃₈O₃S
• 分子量: 406.63
• InChiKey: BPAUXHZXCUJBOX-BKSKZGTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  甲基环戊烯醇酮 在 4-二甲氨基吡啶 、 氢氧化钾 、 lithium aluminium tetrahydride 、 triphenylmethylium hexachloroantimonate(V) 、 二异丁基氢化铝 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 rac-(6R^*)-2-methyl-6-[(4R^*,7aR^*)-7a-methyl-4-(phenylthio)octahydroinden-1-yl]heptan-2-ol
  参考文献：
  名称：

  反式-茚满衍生物的新的非对映选择性方法。25-羟基维生素D 3的前体8-苯基磺酰基-A，B-地胆甾烷衍生物的合成

  摘要：

  描述了六步全合成外消旋体1a，即25-羟基维生素D 3的CD环-侧链片段。

  DOI：

  10.1016/0040-4039(96)01705-4

文献信息

• Enantioselective Total Synthesis of atrans-Hydrindane Rings/Side-Chain Building-Block of Vitamin D− Asymmetric Induction in an Acid-Catalyzed Conjugate-Addition Reaction
  作者：Evgueni Gorobets、Viatcheslav Stepanenko、Jerzy Wicha

  DOI：10.1002/ejoc.200300611

  日期：2004.2

  For the enantioselective total synthesis of 1α,25-dihydroxyvitamin D3 (3), we have developed an enantioselective approach to the “northern” portion building-block 8, starting from the optically active hexanoic acid derivative 44, 2-methylcyclopent-2-en-1-one (10) and 1-(phenylthio)but-3-en-2-one (9). The steric course of the addition reaction of homochiral (S)-ketene acetals 28, 40, 44 and 58 with

  对于 1α,25-二羟基维生素 D3 (3) 的对映选择性全合成，我们开发了一种对“北部”部分构建块 8 的对映选择性方法，从光学活性己酸衍生物 44, 2-methylcyclopent-2-en 开始-1-一 (10) 和 1-(苯硫基)but-3-en-2-one (9)。检查了同手性 (S)-烯酮缩醛 28、40、44 和 58 与 10 的加成反应的空间过程。我们发现，在 28、44 和 40 的情况下，反应以高的简单和诱导（面部）非对映选择性发生。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Diastereoselective Approaches to trans-Hydrindane Derivatives − Total Synthesis of 8-(Phenylsulfonyl)de-A,B-cholestane Precursors to 25-Hydroxyvitamin D3
  作者：Igor Prowotorow、Wiaczesław Stepanenko、Jerzy Wicha

  DOI：10.1002/1099-0690(200208)2002:16<2727::aid-ejoc2727>3.0.co;2-1

  日期：2002.8

  The total diastereoselective synthesis of the C,D rings/side chain building block for the synthesis of 1α,25-dihydroxyvitamin D3 is described. Two tandem Mukaiyama−Michael additions involving silylated ketene acetals derived from tert-butyl 6-methylhept-5-enethioate or tert-butyl 6-methylhept-6-enethioate, 2-methylcyclopent-2-en-1-one, and 1-(phenylthio)but-3-en-2-one afforded the corresponding intermediates

  描述了用于合成 1α,25-二羟基维生素 D3 的 C、D 环/侧链结构单元的总非对映选择性合成。两个串联的 Mukaiyama-Michael 加成涉及衍生自 6-methylhept-5-enethioate 叔丁酯或 6-methylhept-6-enethioate 叔丁酯、2-methylcyclopent-2-en-1-one 和 1-(苯硫基)but-3-en-2-one 得到相应的中间体，其具有目标化合物的完整碳骨架。这些关键中间体的进一步转化包括环化、用 m-CPBA 氧化和还原乙烯基砜部分以提供反式氢化茚环系统。该合成包括五次操作，并在大约 30% 的收率。2-[(苯硫基)甲基]-2-乙烯基[1,3]二氧戊环和2-(苯磺酰基甲基)-2-乙烯基[1, 3]二氧戊环作为迈克尔受体也进行了检查。(© Wiley-VCH Verlag GmbH, 69451 Weinheim,
• Total Synthesis of 25-Hydroxy Vitamin D₃ Northern Portion, Involving Tandem Conjugate Additions
  作者：Stanisław Marczak、Karol Michalak、Zofia Urbańczyk-Lipkowska、Jerzy Wicha

  DOI：10.1021/jo971967x

  日期：1998.4.1

  New approaches to 25-hydroxy vitamin D building blocks 7 and 8 have been developed. Tandem acid-catalyzed conjugate addition of ketene acetal 2d or 2c and acceptors 3 and then 11 yielded 5b (76% from 3) or 22 (64%), respectively, with the proper relative configuration on C20, C17, and C13 (steroid numbering, all compounds are racemic). The trans-hydrindan ring junction in 16 and 27 has been secured by chirality transfer in palladium-catalyzed hydrogenolysis of formates 15 and 26. Treatment of 16 with N-bromoacetamide followed by NaOH yielded a mixture of 8 beta,9 beta- and 8 alpha,9 alpha-epoxides 18 in a ratio of ca. 2:1, which was tosylated and reduced with lithium aluminum hydride without separation. The required diol 20 and its isomer 21 were obtained. In a complementary approach, 27 was oxidized into 8 alpha,9 alpha-epoxide 29 with a new reagent composed of m-CPBA, KF, and 2,6-di-tert-butyl-4-methylphenol. Opening of the epoxide ring in 29 with thiophenoxide anion followed by oxidation afforded dihydroxy sulfone 31. The latter was reduced via the respective dimesylate, and then the protective benzyloxy group was removed yielding 8.
• Enantioselective synthesis of 24,25-dihydroxy vitamin D3 northern portion from (S)-3-hydroxy-2,2-dimethylcyclohexane-1-one. Remote asymmetric induction in an acid-catalysed conjugate addition
  作者：Wiaczeslaw Stepanenko、Jerzy Wicha

  DOI：10.1016/s0040-4039(97)10647-5

  日期：1998.2

  Enantioselective synthesis of building blocks, 2 and 16, for 24,25-dihydroxy- and 25-hydroxy vitamin D synthesis, respectively, from easily accessible optically active hydroxy ketone 5, is described. (C) 1998 Elsevier Science Ltd. All rights reserved.