(4R,4aS,10aR)-6,6,8,8-Tetraisopropyl-4,4a,10,10a-tetrahydro-1,5,7,9-tetraoxa-6,8-disila-benzocycloocten-4-ol | 365569-74-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,4aS,10aR)-6,6,8,8-Tetraisopropyl-4,4a,10,10a-tetrahydro-1,5,7,9-tetraoxa-6,8-disila-benzocycloocten-4-ol
• 英文别名: (6aR,10R,10aS)-2,2,4,4-tetra(propan-2-yl)-6,6a,10,10a-tetrahydropyrano[3,2-f][1,3,5,2,4]trioxadisilocin-10-ol
• CAS: 365569-74-0
• 化学式: C₁₈H₃₆O₅Si₂
• 分子量: 388.652
• InChiKey: GGYDYYLOIKRLJB-KURKYZTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4R,4aS,10aR)-6,6,8,8-Tetraisopropyl-4,4a,10,10a-tetrahydro-1,5,7,9-tetraoxa-6,8-disila-benzocycloocten-4-ol 在 N-溴代丁二酰亚胺(NBS) 、 18-冠醚-6 、 水 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 4.0h， 生成 (6aR,8S,9S,10R,10aR)-10-phenylmethoxy-2,2,4,4-tetra(propan-2-yl)-9-prop-2-enoxy-8-prop-2-enyl-6,6a,8,9,10,10a-hexahydropyrano[3,2-f][1,3,5,2,4]trioxadisilocine
  参考文献：
  名称：

  Convergent synthesis of the ABCDE ring framework of ciguatoxin

  摘要：

  研究表明，烷基化-金属化序列是合成雪卡毒素 1 的 ABCDE 环框架的有效方法。

  DOI：

  10.1039/a903063h
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 吡啶 、 甲醇 、 potassium carbonate 作用下， 生成 (4R,4aS,10aR)-6,6,8,8-Tetraisopropyl-4,4a,10,10a-tetrahydro-1,5,7,9-tetraoxa-6,8-disila-benzocycloocten-4-ol
  参考文献：
  名称：

  Convergent synthesis of the ABCDE ring framework of ciguatoxin

  摘要：

  研究表明，烷基化-金属化序列是合成雪卡毒素 1 的 ABCDE 环框架的有效方法。

  DOI：

  10.1039/a903063h

文献信息

• Concise Synthesis of Ciguatoxin ABC-Ring Fragments and Surface Plasmon Resonance Study of the Interaction of their BSA Conjugates with Monoclonal Antibodies
  作者：Yoko Nagumo、Hiroki Oguri、Yumi Shindo、Shin-ya Sasaki、Tohru Oishi、Masahiro Hirama、Yoshihisa Tomioka、Michinao Mizugaki、Takeshi Tsumuraya

  DOI：10.1016/s0960-894x(01)00358-4

  日期：2001.8

  Monoclonal antibodies (mAbs), 4H2 and 6H7, were prepared previously using a protein conjugate of a 1:1 epimeric mixture of the synthetic ABC-ring fragments or ciguatoxin (CTX), 3 and 4. Here, the interactions of these mAbs with the fragments of CTX and CTX3C, 3 and 5, were investigated by surface plasmon resonance (SPR) spectroscopy in an attempt to clarify an antigenic determinant. Compared with the previous synthesis, the fragment 3 possessing the 2S configuration was synthesized from tri-O-acetyl-D-glucal much more effectively. The mAb 4H2 was already known to show a dose-dependent binding to the bovine serum albumin (BSA) conjugate of 3, bur not to that of 5. The present SPR study of 4H2 demonstrates that the A-ring side chain of 3 plays a decisive role as an epitope. Therefore, SPR can effectively replace the ELISA method for the analysis of mAbs. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy
  作者：Wenpeng Ma、Annika Schmidt、Carsten Strohmann、Charles C. J. Loh

  DOI：10.1002/anie.202405706

  日期：2024.7.15

  The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged as a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility of a phosphonochalcogenide (PCH) catalyst to facilitate access into the challenging, but biologically interesting 7‐membered ring α,α’‐C‐disubstituted oxepane core through an α‐selective strain‐release C‐glycosylation. Methodically, this strategy represents a switch from more common but entropically less desired macrocyclizations to a thermodynamically favored ring‐expansion approach. In light of the general lack of stereoselective methods to access C‐septanosides, a remarkable palette of silyl‐based nucleophiles can be reliably employed in our method. This include a broad variety of useful synthons, such as easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐ketene acetal, silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that a mechanistic shift towards an intramolecular aglycone transposition involving a pentacoordinate silicon intermediate is likely responsible in steering the stereoselectivity.