1-(di-tert-butylhydroxymethyl)-3,3-dimethylcyclopropene

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(di-tert-butylhydroxymethyl)-3,3-dimethylcyclopropene
• 英文别名: 1-di-tert-butylhydroxymethyl-3,3-dimethylcyclopropene；3-(3,3-Dimethylcyclopropen-1-yl)-2,2,4,4-tetramethylpentan-3-ol
• 化学式: C₁₄H₂₆O
• 分子量: 210.36
• InChiKey: NNYYCZAKPWKAEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  四甲基乙二胺 、 1-(di-tert-butylhydroxymethyl)-3,3-dimethylcyclopropene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 生成
  参考文献：
  名称：

  Toward Planar Tetracoordinate Carbon in the Puckered Ladder Structures of Chelated Cyclopropenyllithium Aggregates

  摘要：

  Computational predictions of planar tetracoordinate carbon R(1)R(2)C(alpha)Li(2) arrangements in the cyclopropenyllithium dimer have now realized experimentally in derivatives with additional chelating ligands. The dimer structures of two substituted cyclopropenyllithiums bearing lithium alkoxide and lithium amide side arms, C-alpha and O dilithiated 1-(di-tert-butylhydroxymethyl)-3,3-dimethylcyclopropene (8) as well as C-alpha and N dilithiated 1-(tert-butylaminodimethylsilyl)-3,3-dimethylcyclopropene (9), were characterized by single-crystal X-ray diffraction. The complexes of 8 with tetramethylethylenediamine (TMEDA), (8 . TMEDA)(2), and with THF, (8 . 2THF)(2), show ladder-type dimeric aggregation. The tetracoordinate R(1)R(2)C(alpha)Li(2) carbon environments in both crystal structures have a high degree of planarization (with 35-39 degrees twist angles), partly due to chelation of one of the lithiums by the O- moiety. Compound 9 crystallizes as a dimeric THF solvate, (9 . 2THF)(2) with a puckered ladder structure. Chelation of one of the lithiums by the N- moiety in the individual (9 . 2THF)2 units results in R(1)R(2)C(alpha)Li(2) environments which approach planarity even more closely (17 and 30 degrees twist angles). Bridging of the vinylic C-alpha-C-beta bonds by the chelated lithiums in (9 . 2THF)(2) results in an unexpected feature, the nearly planar tetracoordinate environment of C-beta (the cyclopropene carbon next to ther lithiated site)! Becke3LYP/6-31G* calculations on mixed-anion (MeLi . LiOH)(2) model aggregates are consistent with the experimental findings that dimerization of both (8 . TMEDA)(2) and of (8 . 2THF)(2) involves the Li-O rather than the Li-C bond. In contrast (but also consistent with the model computations and with the steric environments), the (9 . 2THF)(2) dimer is formed via Li-C rather than Li-N bond aggregation.

  DOI：

  10.1021/ja9603362

文献信息

• Towards planar tetracoordinate carbon in the puckered ladder structure of dilithiated 1-di-tert-butylhydroxymethyl-3,3-dimethylcyclopropene
  作者：Klas Sorger、Paul von Ragu� Schleyer、Dietmar Stalke

  DOI：10.1039/c39950002279

  日期：——

  The title compound crystallizes as a THF-solvated dimer with tetracoordinate R1R2CLi2 carbons approaching planarity and unusual C–C lengths in the cyclopropene ring.