(2S,3R)-2-Benzyloxy-5-hydroxy-3-methoxy-cyclohexanone | 902151-30-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3R)-2-Benzyloxy-5-hydroxy-3-methoxy-cyclohexanone
• 英文别名: (2S,3R)-2-(benzyloxy)-5-hydroxy-3-methoxycyclohexanone；(2S,3R)-5-hydroxy-3-methoxy-2-phenylmethoxycyclohexan-1-one
• CAS: 902151-30-8
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: WDKFFJCRVIXYNZ-HIDCPEKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3R)-2-Benzyloxy-5-hydroxy-3-methoxy-cyclohexanone 在 吡啶 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 锂硼氢 、 cerium(III) chloride 、 甲基磺酰氯 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 反应 36.25h， 生成 [(Z,3R,4S,6S,7R)-4,6-bis[[tert-butyl(dimethyl)silyl]oxy]-1-[(1S,5R,6S)-5-methoxy-6-phenylmethoxycyclohex-2-en-1-yl]oxy-3,7-dimethyl-8-phenylmethoxyoct-1-enoxy]-tert-butyl-dimethylsilane
  参考文献：
  名称：

  Synthetic studies toward rapamycin: a solution to a problem in chirality merger through use of the Ireland reaction

  摘要：

  A program directed toward a total synthesis of rapamycin is described. This paper reports the synthesis of enoate 36, a fragment that would correspond to carbons 28-49 of rapamycin. The two building blocks required to reach 36 were allylic alcohol 5 and acid 6. The former was obtained in a straightforward way from D-(+)-glucose. The route passed through a 5,6-methylene derivative (see structure 12) that underwent Ferrier transformation to the hydroxycyclohexanone derivative 13. The acid 6 was built from aldehyde 15. An addition reaction of allyltrimethylsilane to 15 and a subsequent addition of crotylboronate 18 to aldehyde 17 were the key steps in the chain extension leading to the acid. The central issue of the synthesis was the merging of two chiral sectors (see A and B) to produce an ensemble in which the achiral spacer element consists of a single methylene carbon, C39. This problem was solved by establishing an ester bond between 5 and 6. The strategic C40-C39 carbon-carbon bond was generated by application of the Ireland ester enolate rearrangement. The extraneous carboxyl group (see structure 28) was removed by photolysis of the N-hydroxyphthalimide ester (see transformation 30 --> 31).

  DOI：

  10.1021/jo00020a026
• 作为产物：
  描述：

  Methyl 2-deoxy-3-O-methyl-6-O-triphenylmethyl-α-D-arabino-hexopyranoside 在 咪唑 、 camphor-10-sulfonic acid 、 碘 、 mercury(II) trifluoroacetate 、 sodium hydride 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 生成 (2S,3R)-2-Benzyloxy-5-hydroxy-3-methoxy-cyclohexanone
  参考文献：
  名称：

  Novel γ-secretase inhibitors discovered by library screening of in-house synthetic natural product intermediates

  摘要：

  Screening of our in-house compound library comprised of intermediates of natural product synthesis projects resulted in discovering two novel gamma-secretase inhibitors, which coincidently had similar moieties, that is, cyclohexenone and two aryl groups arranged on the core six-membered ring. Structure-activity relationship studies of these compounds were also developed. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2006.04.025

文献信息

• Novel γ-secretase inhibitors discovered by library screening of in-house synthetic natural product intermediates
  作者：Yasuko Takahashi、Haruhiko Fuwa、Akane Kaneko、Makoto Sasaki、Satoshi Yokoshima、Hifumi Koizumi、Tohru Takebe、Toshiyuki Kan、Takeshi Iwatsubo、Taisuke Tomita、Hideaki Natsugari、Tohru Fukuyama

  DOI：10.1016/j.bmcl.2006.04.025

  日期：2006.7

  Screening of our in-house compound library comprised of intermediates of natural product synthesis projects resulted in discovering two novel gamma-secretase inhibitors, which coincidently had similar moieties, that is, cyclohexenone and two aryl groups arranged on the core six-membered ring. Structure-activity relationship studies of these compounds were also developed. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthetic studies toward rapamycin: a solution to a problem in chirality merger through use of the Ireland reaction
  作者：Matthew J. Fisher、Cheryl D. Myers、Jesus Joglar、Shu Hui Chen、Samuel J. Danishefsky

  DOI：10.1021/jo00020a026

  日期：1991.9

  A program directed toward a total synthesis of rapamycin is described. This paper reports the synthesis of enoate 36, a fragment that would correspond to carbons 28-49 of rapamycin. The two building blocks required to reach 36 were allylic alcohol 5 and acid 6. The former was obtained in a straightforward way from D-(+)-glucose. The route passed through a 5,6-methylene derivative (see structure 12) that underwent Ferrier transformation to the hydroxycyclohexanone derivative 13. The acid 6 was built from aldehyde 15. An addition reaction of allyltrimethylsilane to 15 and a subsequent addition of crotylboronate 18 to aldehyde 17 were the key steps in the chain extension leading to the acid. The central issue of the synthesis was the merging of two chiral sectors (see A and B) to produce an ensemble in which the achiral spacer element consists of a single methylene carbon, C39. This problem was solved by establishing an ester bond between 5 and 6. The strategic C40-C39 carbon-carbon bond was generated by application of the Ireland ester enolate rearrangement. The extraneous carboxyl group (see structure 28) was removed by photolysis of the N-hydroxyphthalimide ester (see transformation 30 --> 31).