1-[(Z)-(1,3-dimethyl-2-bora-1,3-diazacyclopent-2-yl)methylidene]-2-[(Z)-(trimethylstannyl)methylidene]cyclopentane | 197775-74-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 1-[(Z)-(1,3-dimethyl-2-bora-1,3-diazacyclopent-2-yl)methylidene]-2-[(Z)-(trimethylstannyl)methylidene]cyclopentane
• 英文别名: [(Z)-[(2Z)-2-[(1,3-dimethyl-1,3,2-diazaborolidin-2-yl)methylidene]cyclopentylidene]methyl]-trimethylstannane
• CAS: 197775-74-9
• 化学式: C₁₄H₂₇BN₂Sn
• 分子量: 352.903
• InChiKey: DHMMUJHDFBJCHO-CEXPOERHSA-N

物化性质

• 沸点：
  340.8±52.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-溴代丁二酰亚胺(NBS) 、 频哪醇 、 1-[(Z)-(1,3-dimethyl-2-bora-1,3-diazacyclopent-2-yl)methylidene]-2-[(Z)-(trimethylstannyl)methylidene]cyclopentane 在 catalyst: p-toluenesulfonic acid 作用下， 以 氯仿 为溶剂， 生成 2-((Z)-((Z)-2-(bromomethylene)cyclopentylidene)methyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Stereoselective Cyclization of Functionalized 1,n-Diynes Mediated by [X−Y] Reagents [X−Y = R₃Si−SnR′₃ or (R₂N)₂B−SnR′₃]: Synthesis and Properties of Atropisomeric 1,3-Dienes

  摘要：

  The borylstannane [-N(Me)CH2CH2(Me)N-]B-SnMe3 is a superior reagent capable of effecting bisfunctionalization-cyclization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dipropargylbenzenes, 2,2'-dipropargylbiphenyls, 4,5-dipropargyldioxolanes, and 1,4-dipropargyl-beta -lactams) where the more well-known silylstannanes fail. Variable-temperature NMR studies showed that conformational restraints imposed by selected backbones increase the activation barrier for the helical isomerization in (Z,2)-dienes that are generated in the cyclization of the diynes. In the biphenyl and dioxolane systems, the reactions proceed with surprisingly good regio- and stereoselectivity. The resulting diazaborolidine derivatives are hydrolytically unstable but can be isolated by recrystallization or precipitation. For further synthetic applications, it is advantageous to convert these compounds in situ into the corresponding dioxaborolidines with either retention of the Me3Sn group or replacement of this group via halodestannylation. The configurations of the vinyl moieties are preserved in these reactions. Highly functionalized dibenzocyclooctadienes, which adorn the carbon frames of several important cytotoxic natural products, can be synthesized using this chemistry.

  DOI：

  10.1021/ja105939v
• 作为产物：
  描述：

  1,3-dimethyl-1,3,2λ²-diazaborolidine,trimethyltin 、 1,6-庚二炔 在 四(三苯基膦)钯 作用下， 以 苯 为溶剂， 生成 1-[(Z)-(1,3-dimethyl-2-bora-1,3-diazacyclopent-2-yl)methylidene]-2-[(Z)-(trimethylstannyl)methylidene]cyclopentane
  参考文献：
  名称：

  钯催化的二炔和烯炔化合物的硼烷基锡烷基化碳环化

  摘要：

  二炔的高度区域选择性和立体选择性borylstannylative carbocyclization 2A - ˚F与borylstannane 1被有效地由一系列钯络合物如Cl在室温下催化2的Pd（PPh 3）2，氯2的Pd [P（邻甲苯基）3 ] 2，Pd（PPh 3）4和Pd（dba）2，以高收率得到1-（硼烷基亚甲基）-2-（锡烷基亚甲基）环烷烃衍生物3a - f。1，6-烯炔（2g）的反应也相似，可提供高产率的相应环化产物3克。

  DOI：

  10.1021/om970704q