(R)-(+)-benzyl-tertbutylphenylphosphine-borane | 952055-39-9

• 英文名称: (R)-(+)-benzyl-tertbutylphenylphosphine-borane
• CAS: 952055-39-9
• 化学式: C₁₇H₂₄BP
• 分子量: 270.162
• InChiKey: IADXYOWIHLYWOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  19.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  tert-Butylphenylphosphine oxide 在 sodium tetrahydroborate 、 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.33h， 生成 (R)-(+)-benzyl-tertbutylphenylphosphine-borane
  参考文献：
  名称：

  Bulky, Optically Active P-Stereogenic Phosphine–Boranes from Pure H-Menthylphosphinates

  摘要：

  The transformation of readily available pure-H-menthylphosphinates into chiral phosphinous acid-boranes permits the elaboration of bulky P-stereogenic secondary phosphine-boranes. Taking advantage of the synthetic potential of these compounds, a broad range of hindered P-chiral tertiary phosphine-boranes has been prepared with excellent enantiomeric excesses. The utility of bulky o-tolylphosphines was illustrated by the synthesis of a rare enantiopure phosphapalladacycle (S-P,S-P)-12.

  DOI：

  10.1021/ja2034816

文献信息

• In Situ Dearomatisation/Alkylation of Arylphosphane Derivatives
  作者：Marek Stankevič、Karolina Wójcik、Magdalena Jaklińska、K. Michał Pietrusiewicz

  DOI：10.1002/ejoc.201200096

  日期：2012.5

  The dearomatisation of aryldialkylphosphane–boranes and aryldialkylphosphane oxides under Birch reduction conditions, followed by treatment with reactive alkyl halides, provides the corresponding α-functionalised (cyclohexa-1,4-dien-3-yl)phosphane derivatives. This reaction offers a method of choice for the synthesis of bulky (cyclohexadienyl)phosphanes.

  芳基二烷基膦-硼烷和芳基二烷基膦氧化物在 Birch 还原条件下脱芳构化，然后用反应性烷基卤化物处理，提供相应的 α-官能化（环六-1,4-二烯-3-基）膦衍生物。该反应为合成大体积（环己二烯基）膦提供了一种选择方法。
• Racemization mechanism of lithium <i>tert</i> ‐butylphenylphosphido‐borane: A kinetic insight
  作者：Rémy Fortrie、David Gatineau、Damien Hérault、Aurélie Béal、Jean‐Valère Naubron、Laurent Giordano、Gérard Buono

  DOI：10.1002/chir.23383

  日期：2022.1

  The racemization mechanism of tert-butylphenylphosphido-borane is investigated experimentally and theoretically. Based on this converging approach, it is shown, first, that several phosphido-borane molecular species coexist at the time of the reaction and, second, that one particular of both initially assumed reactive routes most significantly contribute to the overall racemization process. From our

  对叔丁基苯基磷硼烷的消旋机理进行了实验和理论研究。基于这种趋同方法，首先表明几种磷化硼烷分子物种在反应时共存，其次，两种最初假定的反应路线中的一个对整个消旋过程的贡献最大。从我们的收敛建模和实验测量中可以看出，这里最可能遇到的物种是磷化硼烷-Li (THF) 2中性溶剂化物，其 P-立体中心单分子通过 Y 形过渡结构反转（Δ r G° ≠ : 81 kJ mol -1) 对消旋过程的贡献最大。
• Direct Synthesis of Tertiary Phosphines via Alkoxide-Mediated Deborylative Phosphination of Organoboronates
  作者：Huaxing Sun、Jing Wang、Zihang Du、Kun Zhang、Jiefeng Hu、Su Jing

  DOI：10.1021/acs.orglett.4c00001

  日期：2024.3.1

  carbon–heteroatom bonds. However, its potential application in the formation of carbon and phosphorus remains unexplored. In this study, we present an alkoxide base-promoted reaction system that enables deborylative phosphination of benzylic organoboronates and geminal bis(boronates) via selective C–B bond cleavage. This approach allows for the synthesis of valuable tertiary phosphines in good yields under

  烷基硼的直接转化已成为创建碳-碳和碳-杂原子键的通用且强大的方法。然而，其在碳和磷形成中的潜在应用仍未得到探索。在这项研究中，我们提出了一种醇盐碱促进的反应系统，该系统能够通过选择性 C-B 键断裂对苄基有机硼酸酯和偕双（硼酸酯）进行脱硼基膦化。这种方法可以在温和条件下以良好的产率合成有价值的叔膦。该方法的实用性和工业潜力通过操作简单性、广泛的基质范围和易于扩展性得到强调。
• Alkylation of Phosphine Boranes by Phase-Transfer Catalysis
  作者：Hélène Lebel、Sébastien Morin、Valérie Paquet

  DOI：10.1021/ol0347139

  日期：2003.6.1

  [GRAPHICS]The alkylation of phosphine boranes with various electrophiles proceeds with good to excellent yields in a biphasic solution in the presence of tetrabutylammonium bromide as a phase-transfer catalyst.
• The Hydroxyalkyl Moiety As a Protecting Group for the Stereospecific Alkylation of Masked Secondary Phosphine-Boranes
  作者：Sébastien Lemouzy、Marion Jean、Laurent Giordano、Damien Hérault、Gérard Buono

  DOI：10.1021/acs.orglett.5b03450

  日期：2016.1.4

  The synthesis of functionalized tertiary phosphine-boranes has been developed via a chemodivergent approach from readily accessible (hydroxymethyl) phosphine-boranes under mild conditions. O-Alkylation or decarbonylative P-alkylation product could be exclusively obtained. The P-alkylation reaction was found to proceed in moderate to very good yields and very high enantiospecificity (es >95%) using a variety of alkyl halides as electrophiles. The configurational stability of the sodium phosphido-borane intermediate was also investigated and allowed a deeper understanding of the reaction mechanism, furnishing secondary phosphine-boranes in moderate yield and enantiopurity.