(1R,7S)-9,9-di-tert-butyl-2,8,10-trioxa-9-silabicyclo[5.4.0]undec-3,5-diene

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1R,7S)-9,9-di-tert-butyl-2,8,10-trioxa-9-silabicyclo[5.4.0]undec-3,5-diene
• 英文别名: (4aR,9aS)-2,2-ditert-butyl-4a,9a-dihydro-4H-[1,3,2]dioxasilino[5,4-b]oxepine
• 化学式: C₁₅H₂₆O₃Si
• 分子量: 282.455
• InChiKey: LYZZYTDRXFSDKH-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4,6-O-di(tert-butyl)silanediyl-D-glucal 在 三乙基硅烷 、 4-二甲氨基吡啶 、 三氟甲磺酸三甲基硅酯 、 diethylzinc 作用下， 以 吡啶 、 乙醚 、 正己烷 、 乙腈 为溶剂， 反应 6.5h， 生成 (1R,7S)-9,9-di-tert-butyl-2,8,10-trioxa-9-silabicyclo[5.4.0]undec-3,5-diene
  参考文献：
  名称：

  Formation of Seven-Membered Oxacycles through Ring Expansion of Cyclopropanated Carbohydrates

  摘要：

  The cyclopropanation and ring expansion of 4,6-O-(di-tert-butylsilanediyl)-D-glucal (1) to produce oxepanes have been investigated. Using catalytic amounts of TMSOTf and an excess of a silylated nucleophile, a wide range of substituted oxepanes have been synthesized. Good to excellent yields are obtained; however, only modest diastereoselectivity resulted. This new methodology should provide convenient access into the synthesis of optically active oxepanes.

  DOI：

  10.1021/jo970649v

文献信息

• Synthesis and Properties of Oligonucleotides Containing A 7-Membered (Oxepane) Sugar Ring
  作者：David Sabatino、Masad J. Damha

  DOI：10.1080/15257770701527760

  日期：2007.11.26

  Herein we describe the synthesis of novel 7-membered ring (oxepane) thymine and adenine nucleosides (oT and oA) and their corresponding 5′-O-phosphoramidite derivatives. Two homopolymeric sequences (oT 15 and oA 15 ) were prepared via conventional solid-phase synthesis. The mutually complementary strands had the ability to form a duplex (oT 15 :oA 15 ) exhibiting a transition temperature of 12°C. The

  在此，我们描述了新型 7 元环（氧杂环庚烷）胸腺嘧啶和腺嘌呤核苷（oT 和 oA）及其相应的 5'-O-亚磷酰胺衍生物的合成。两种均聚物序列（oT 15 和oA 15 ）通过常规固相合成制备。相互互补的链能够形成双链体（oT 15 :oA 15 ），转变温度为12°C。还发现氧杂环庚烷寡核苷酸与其各自的互补 RNA 链相关联，从而形成 oT 15 :rA 15 (13°C) 和 oA 15:rU 15 (12°C) 杂交体。相应的天然双链体，即 dT 15 :dA 15 、dT 15 :rA 15 和 dA 15 :rU 15 的熔解温度分别为 37°C、32°C 和 16°C。oT 15 :rA 15 的 CD 谱与天然 dT 15 :rA15 杂交的 CD 谱非常相似，事实上，
• WO2007/25043
  申请人：——

  公开号：——

  公开（公告）日：——
• Formation of Seven-Membered Oxacycles through Ring Expansion of Cyclopropanated Carbohydrates
  作者：John O. Hoberg

  DOI：10.1021/jo970649v

  日期：1997.9.1

  The cyclopropanation and ring expansion of 4,6-O-(di-tert-butylsilanediyl)-D-glucal (1) to produce oxepanes have been investigated. Using catalytic amounts of TMSOTf and an excess of a silylated nucleophile, a wide range of substituted oxepanes have been synthesized. Good to excellent yields are obtained; however, only modest diastereoselectivity resulted. This new methodology should provide convenient access into the synthesis of optically active oxepanes.