Tri-sec-butylborhydrid-Anion

• 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: Tri-sec-butylborhydrid-Anion
• 英文别名: Tri-sec.-butylborhydrid；Tri(butan-2-yl)boranuide
• 化学式: C₁₂H₂₈B
• 分子量: 183.165
• InChiKey: KFIBZZRAZVBBOQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.61
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tricarbonyl(η(4)-buta-1,3-diene)iron 、 Tri-sec-butylborhydrid-Anion 以 not given 为溶剂， 生成
  参考文献：
  名称：

  （二烯）三羰基铁络合物的氢化物还原反应，以取代取代的（烯丙基）三羰基铁阴离子。用Et3BH-检测甲酰中间体在氢化（1,3-丁二烯）三羰基铁中的甲酰中间体

  摘要：

  Reactions of (butadiene)iron tricarbonyl or (1-phenylbutadiene)iron tricarbonyl with Et3BH-in tetrahydrofuran monitored by IR spectroscopy showed efficient conversion to the corresponding (allyl)iron tricarbonyl anions (CH3CH---CH---CH2)Fe(CO)3- and (CH3CH---CH-CHC6H5)Fe(CO)3-. Treatment of these solutions with (CH3)3SnCl resulted in formation of (anti-methallyl)Fe(CO)3-SnMe3, anti-12 and (anti-1-methyl-syn-3-phenylallyl)Fe(CO)3-SnMe3, anti,syn-13. These anti isomers thermally isomerize to their syn isomers by clean first-order kinetics (anti-12 to syn-12, k = 2.6 x 10(-5) s-1, 55-degrees-C; anti,syn-13 to syn,syn-13, k = 5.8 x 10(-6) s-1, 25-degrees-C). The sterochemistry of syn,syn-13 was confirmed by X-ray analysis (monoclinic, P2(1/n), a = 14.830(3) angstrom, b = 7.5651(18) angstrom, c = 15.7202(18) angstrom, beta = 102.001(13)-degrees, Z = 4). Treatment of the (allyl)iron tin complexes anti-12, syn-12, anti,syn-13, and syn,syn-13 with KH results in clean formation of the corresponding (allyl)iron tricarbonyl anions which can be isolated in good yields as their potassium salts. The configuration of the allyl unit is maintained in the reduction reaction. Low temperature H-1, H-2, and C-13 NMR experiments reveal that the anionic formyl complex (C4H6)(CO)2FeCHO- is an intermediate in the formation of (anti-methallyl)Fe(CO)3- from Et3BH- and (butadiene)iron tricarbonyl. Hydride migration from formyl to C1 of the butadiene ligand occurs at -50-degrees-C, k = 8.3 x 10(-5) s-1, DELTAG(double dagger) = 17 kcal/mol.

  DOI：

  10.1021/om00033a041
• 作为试剂：
  描述：

  纳洛酮 在 Tri-sec-butylborhydrid-Anion 作用下， 生成 6alpha-纳洛醇
  参考文献：
  名称：

  6β-纳曲醇和6α-纳曲醇的C环构象。来自质子和碳13核磁共振的证据。

  摘要：

  DOI：

  10.1021/jo00883a027

文献信息

• Hydride reduction of (diene)iron tricarbonyl complexes as a route to substituted (allyl)iron tricarbonyl anions. Detection of a formyl intermediate in the hydride reduction of (1,3-butadiene)iron tricarbonyl by Et3BH-
  作者：Seok Chang、Peter S. White、Maurice Brookhart

  DOI：10.1021/om00033a041

  日期：1993.9

  Reactions of (butadiene)iron tricarbonyl or (1-phenylbutadiene)iron tricarbonyl with Et3BH-in tetrahydrofuran monitored by IR spectroscopy showed efficient conversion to the corresponding (allyl)iron tricarbonyl anions (CH3CH---CH---CH2)Fe(CO)3- and (CH3CH---CH-CHC6H5)Fe(CO)3-. Treatment of these solutions with (CH3)3SnCl resulted in formation of (anti-methallyl)Fe(CO)3-SnMe3, anti-12 and (anti-1-methyl-syn-3-phenylallyl)Fe(CO)3-SnMe3, anti,syn-13. These anti isomers thermally isomerize to their syn isomers by clean first-order kinetics (anti-12 to syn-12, k = 2.6 x 10(-5) s-1, 55-degrees-C; anti,syn-13 to syn,syn-13, k = 5.8 x 10(-6) s-1, 25-degrees-C). The sterochemistry of syn,syn-13 was confirmed by X-ray analysis (monoclinic, P2(1/n), a = 14.830(3) angstrom, b = 7.5651(18) angstrom, c = 15.7202(18) angstrom, beta = 102.001(13)-degrees, Z = 4). Treatment of the (allyl)iron tin complexes anti-12, syn-12, anti,syn-13, and syn,syn-13 with KH results in clean formation of the corresponding (allyl)iron tricarbonyl anions which can be isolated in good yields as their potassium salts. The configuration of the allyl unit is maintained in the reduction reaction. Low temperature H-1, H-2, and C-13 NMR experiments reveal that the anionic formyl complex (C4H6)(CO)2FeCHO- is an intermediate in the formation of (anti-methallyl)Fe(CO)3- from Et3BH- and (butadiene)iron tricarbonyl. Hydride migration from formyl to C1 of the butadiene ligand occurs at -50-degrees-C, k = 8.3 x 10(-5) s-1, DELTAG(double dagger) = 17 kcal/mol.