B-cyclopropanyl-9-borabicyclo[3.3.1]nonane | 23418-79-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: B-cyclopropanyl-9-borabicyclo[3.3.1]nonane
• 英文别名: B-cyclopropyl-9-borabicyclo[3.3.1]nonane；B-cyclopropyl-(9-BBN)；B-cyclopropyl-9-BBN；9-Borabicyclo[3.3.1]nonane, 9-cyclopropyl-；9-cyclopropyl-9-borabicyclo[3.3.1]nonane
• CAS: 23418-79-3
• 化学式: C₁₁H₁₉B
• 分子量: 162.083
• InChiKey: HWFHFPGRVIBGLV-UHFFFAOYSA-N

物化性质

• 沸点：
  96 °C(Press: 11 Torr)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  3.0
• 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：
  0

反应信息

• 作为反应物：
  描述：

  B-cyclopropanyl-9-borabicyclo[3.3.1]nonane 、 1-benzyl-tetrahydro-thiophenium tetrafluoroborate 在 lithium hexamethyldisilazane 、 sodium hydroxide 、 双氧水 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 以89%的产率得到1-phenyl-1-(5-hydroxycyclooctyl)methanol
  参考文献：
  名称：

  Asymmetric Sulfur Ylide Reactions with Boranes:  Scope and Limitations, Mechanism and Understanding

  摘要：

  The reactions of aryl-stabilized sulfur ylides with organoboranes has been studied under a variety of conditions. At 5 or -78 degrees C, the reaction with Et3B gave a mixture of the first and second homologation products, but at -100 degrees C, only the first homologation product was obtained even with just 1.1 equiv of Et3B. Under these optimized conditions, the chiral sulfur ylides (derived from camphor sulfonic acid) with different aryl groups were reacted with Et3B to give the corresponding alcohols (95-98% yield, 96-98% ee) and amines (74-77% yield, > 98% ee). The origin of the high enantioselectivity is discussed. The use of nonsymmetrical 9-BBN derivatives was also explored. It was found that whereas primary alkyl substituents gave mixtures of products derived from competing migration of the boron substituent and the boracycle, all other groups resulted in either exclusive migration of the boron substituent (Ph, hexenyl, i-Pr) or exclusive migration of the boracycle (hexynyl, cyclopropyl). The factors responsible for the outcome of the reactions involving a hindered (i-Pr) and an unhindered (propynyl) substituent were studied by DFT calculations. This revealed that, in the case of an unhindered substituent, the conformation of the ate complex is the dominant factor whereas, in the case of a hindered substituent, the barriers to interconversion between the conformers of the ate complex and subsequent migration control the outcome of the reaction.

  DOI：

  10.1021/ja074110i
• 作为产物：
  描述：

  9-硼双环[3.3.1]壬烷 以 四氢呋喃 为溶剂， 150.0 ℃ 、399.97 Pa 条件下， 反应 12.75h， 生成 B-cyclopropanyl-9-borabicyclo[3.3.1]nonane
  参考文献：
  名称：

  A versatile synthesis of 9-BBN derivatives from organometallic reagents and 9-(triisopropylsilyl)thio-9-borabicyclo[3.3.1]nonane

  摘要：

  Representative B-substituted-9-BBNs (3) are efficiently prepared from either organolithium or Grignard reagents through their addition to (TIPS)S-9-BBN (1) which is readily available from TIPSSH and 9-BBN-H. The thermally induced collapse of the intermediate 'ate' complexes (2) produces 3 which is easily isolated in good yield and high purity. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00450-0

文献信息

• The Enantioselective Synthesis of α-Amino Acid Derivatives via Organoboranes
  作者：Martin J. O'Donnell、Mark D. Drew、Jeremy T. Cooper、Francisca Delgado、Changyou Zhou

  DOI：10.1021/ja017522e

  日期：2002.8.1

  Optically active (S)-α-amino acids are prepared in 54−95% ee (12 cases) by reaction of the Schiff base acetate of glycine tert-butyl ester with B-alkyl-9-BBN derivatives in the presence of the Cinc...

  通过甘氨酸叔丁酯的席夫碱乙酸酯与 B-烷基-9-BBN 衍生物在 Cinc 存在下反应，以 54-95% ee（12 例）制备光学活性 (S)-α-氨基酸...
• 10.1002/anie.202408419
  作者：Chen, Donghuang、Lepori, Clément、Guillot, Régis、Gil, Richard、Bezzenine, Sophie、Hannedouche, Jérôme

  DOI：10.1002/anie.202408419

  日期：——

  A well-defined iron catalyst with high efficiency for Suzuki–Miyaura coupling involving C(sp3) partners is described. In the presence of a lithium amide base, this catalyst enabled, for the first time, C(sp3)−C(sp2) coupling of 1°, 2°, and 3° alkyl halides and (hetero)aryl boronic esters as well as C(sp3)−C(sp3) coupling of 1° and 2° alkyl halides and 1° and 2° alkyl boranes under mild conditions and

  描述了一种明确的铁催化剂，具有高效率，适用于涉及 C(sp 3 ) 伴侣的 Suzuki-Miyaura 偶联。在氨基锂碱存在下，该催化剂首次实现了 1°、2° 和 3° 卤代烷与（杂）芳基硼酸酯的 C(sp 3 )−C(sp 2 ) 偶联：以及在温和条件下和具有广泛官能团耐受性的 1° 和 2° 烷基卤化物与 1° 和 2° 烷基硼烷的 C(sp 3 )−C(sp 3 ) 偶联。
• Catalytic Asymmetric γ-Alkylation of Carbonyl Compounds via Stereoconvergent Suzuki Cross-Couplings
  作者：Susan L. Zultanski、Gregory C. Fu

  DOI：10.1021/ja2079515

  日期：2011.10.5

  With the aid of a chiral nickel catalyst, enantioselective gamma- (and delta-) alkylations of carbonyl compounds can be achieved through the coupling of gamma-haloamides with alkylboranes. In addition to primary alkyl nucleophiles, for the first time for an asymmetric cross-coupling of an unactivated alkyl electrophile, an arylmetal, a boronate ester, and a secondary (cyclopropyl) alkylmetal compound are shown to couple with significant enantioselectivity. A mechanistic study indicates that cleavage of the carbon-halogen bond of the electrophile is irreversible under the conditions for asymmetric carbon-carbon bond formation.
• CHA, JIN SOON;YOON, MAL SOOK;LEE, KWANG WOO;LEE, JAE CHEOL, HETEROCYCLES, 27,(1988) N, C. 1455-1460
  作者：CHA, JIN SOON、YOON, MAL SOOK、LEE, KWANG WOO、LEE, JAE CHEOL

  DOI：——

  日期：——
• Asymmetric Sulfur Ylide Reactions with Boranes:  Scope and Limitations, Mechanism and Understanding
  作者：Guang Y. Fang、Olov A. Wallner、Nadia Di Blasio、Xavier Ginesta、Jeremy N. Harvey、Varinder K. Aggarwal

  DOI：10.1021/ja074110i

  日期：2007.11.28

  The reactions of aryl-stabilized sulfur ylides with organoboranes has been studied under a variety of conditions. At 5 or -78 degrees C, the reaction with Et3B gave a mixture of the first and second homologation products, but at -100 degrees C, only the first homologation product was obtained even with just 1.1 equiv of Et3B. Under these optimized conditions, the chiral sulfur ylides (derived from camphor sulfonic acid) with different aryl groups were reacted with Et3B to give the corresponding alcohols (95-98% yield, 96-98% ee) and amines (74-77% yield, > 98% ee). The origin of the high enantioselectivity is discussed. The use of nonsymmetrical 9-BBN derivatives was also explored. It was found that whereas primary alkyl substituents gave mixtures of products derived from competing migration of the boron substituent and the boracycle, all other groups resulted in either exclusive migration of the boron substituent (Ph, hexenyl, i-Pr) or exclusive migration of the boracycle (hexynyl, cyclopropyl). The factors responsible for the outcome of the reactions involving a hindered (i-Pr) and an unhindered (propynyl) substituent were studied by DFT calculations. This revealed that, in the case of an unhindered substituent, the conformation of the ate complex is the dominant factor whereas, in the case of a hindered substituent, the barriers to interconversion between the conformers of the ate complex and subsequent migration control the outcome of the reaction.