<2R,3R,4R,N(3R)>-4-(dimethylamino)-N-<3-(4-hydroxymethyl-2-oxazolyl)butyl>-5-methoxy-2,3-bis((triethylsilyl)oxy)valeramide | 139462-41-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: <2R,3R,4R,N(3R)>-4-(dimethylamino)-N-<3-(4-hydroxymethyl-2-oxazolyl)butyl>-5-methoxy-2,3-bis((triethylsilyl)oxy)valeramide
• 英文别名: (2R,3R,4R)-4-dimethylamino-5-methoxy-N-(3R-((4-hydroxymethyl)-2-oxazolyl)-1-butyl)-2,3-di((triethylsilyl)oxy)pentamide；(2R,3R,4R)-4-(dimethylamino)-N-[(3R)-3-[4-(hydroxymethyl)-1,3-oxazol-2-yl]butyl]-5-methoxy-2,3-bis(triethylsilyloxy)pentanamide
• CAS: 139462-41-2
• 化学式: C₂₈H₅₇N₃O₆Si₂
• 分子量: 587.948
• InChiKey: NZLCPXRWNSSSTI-VNSJUHMKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.13
• 重原子数：
  39
• 可旋转键数：
  21
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  106
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  <2R,3R,4R,N(3R)>-4-(dimethylamino)-N-<3-(4-hydroxymethyl-2-oxazolyl)butyl>-5-methoxy-2,3-bis((triethylsilyl)oxy)valeramide 在 2,6-二甲基吡啶 、 四溴化碳 、 三苯基膦 作用下， 以 乙腈 为溶剂， 以83%的产率得到<2R,3R,4R,N(3R)>-4-(dimethylamino)-N-<3-(4-bromomethyl-2-oxazolyl)butyl>-5-methoxy-2,3-bis((triethylsilyl)oxy)valeramide
  参考文献：
  名称：

  Asymmetric synthesis of calyculin A. 2. The C26-C37 .gamma.-amino acid fragments

  摘要：

  New chiral imide enolate alkylation, aldol, and Michael addition bond constructions have been employed in the asymmetric synthesis of the C26-C37 portion of calyculin A.

  DOI：

  10.1021/jo00033a010
• 作为产物：
  描述：

  <2R,3R,4R,N(3R)>-4-(dimethylamino)-N-<3-(4-carbomethoxy-2-oxazolyl)butyl>-5-methoxy-2,3-bis((triethylsilyl)oxy)valeramide 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.5h， 以75%的产率得到<2R,3R,4R,N(3R)>-4-(dimethylamino)-N-<3-(4-hydroxymethyl-2-oxazolyl)butyl>-5-methoxy-2,3-bis((triethylsilyl)oxy)valeramide
  参考文献：
  名称：

  Applications of crotyldiisopinocampheylboranes in synthesis: a formal total synthesis of (+)-calyculin A

  摘要：

  报道了海洋代谢产物（+）-卡伊库林A的正式全合成。关键步骤包括（i）使用布朗烯丙基硼化化学来控制同型烯醇阵列的相对和绝对立体化学，从而设置所需的八个立体中心；（ii）在构建天然产物的氰基四烯单元中使用斯蒂尔偶联方法；以及（iii）一种改良的Cornforth-Meyers方法来合成噁唑片段。关键词：卡伊库林，海洋天然产物，磷酸酶抑制剂，全合成，钯催化偶联反应，烯丙基硼化反应，醛缩反应，螺环醚，Cornforth-Meyers噁唑反应。

  DOI：

  10.1139/v01-133

文献信息

• Asymmetric synthesis of calyculin A. 2. The C26-C37 .gamma.-amino acid fragments
  作者：David A. Evans、James R. Gage、James L. Leighton、Annette S. Kim

  DOI：10.1021/jo00033a010

  日期：1992.3

  New chiral imide enolate alkylation, aldol, and Michael addition bond constructions have been employed in the asymmetric synthesis of the C26-C37 portion of calyculin A.
• Total synthesis of (+)-calyculin A
  作者：David A. Evans、James R. Gage、James L. Leighton

  DOI：10.1021/ja00050a024

  日期：1992.11

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.
• Applications of crotyldiisopinocampheylboranes in synthesis: a formal total synthesis of (+)-calyculin A
  作者：Oren P Anderson、Anthony GM Barrett、Jeremy J Edmunds、Shun-Ichiro Hachiya、James A Hendrix、Kiyoshi Horita、James W Malecha、Christopher J Parkinson、Andrew VanSickle

  DOI：10.1139/v01-133

  日期：2001.11.1

  The formal total synthesis of the marine metabolite (+)-calyculin A is reported. The key steps involve (i) the use of Brown allylboration chemistry to control the relative and absolute stereochemistry of homoallylic alcohol arrays, thus setting eight of the desired stereocenters; (ii) Stille coupling methodology in the construction of the cyano tetraene unit of the natural product; and (iii) a modified Cornforth–Meyers approach to the synthesis of the oxazole fragment.Key words: calyculin, marine natural product, phosphatase inhibitor, total synthesis, palladium catalyzed coupling reactions, allylboration reactions, aldol reactions, spiroketal, Cornforth–Meyers oxazole reaction.

  报道了海洋代谢产物（+）-卡伊库林A的正式全合成。关键步骤包括（i）使用布朗烯丙基硼化化学来控制同型烯醇阵列的相对和绝对立体化学，从而设置所需的八个立体中心；（ii）在构建天然产物的氰基四烯单元中使用斯蒂尔偶联方法；以及（iii）一种改良的Cornforth-Meyers方法来合成噁唑片段。关键词：卡伊库林，海洋天然产物，磷酸酶抑制剂，全合成，钯催化偶联反应，烯丙基硼化反应，醛缩反应，螺环醚，Cornforth-Meyers噁唑反应。