(phenylethynyl)di-t-butylphosphine | 66128-15-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (phenylethynyl)di-t-butylphosphine
• 英文别名: PBu(t)2(CCC6H5)；Ditert-butyl(2-phenylethynyl)phosphane
• CAS: 66128-15-2
• 化学式: C₁₆H₂₃P
• 分子量: 246.332
• InChiKey: NAJRRNNGPUPTCL-UHFFFAOYSA-N

物化性质

• 沸点：
  319.3±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  Co2(CO)4(μ-CO)2(μ-bis(diphenylphosphino)methane) 、 (phenylethynyl)di-t-butylphosphine 在 Pd(O₂CCH₃)2 作用下， 以 氘代四氢呋喃 、 甲苯 为溶剂， 生成 [(μ-bis(diphenylphosphino)methane)Co2(CO)4][μ,η-PhCCP(O)(t-Bu)2]
  参考文献：
  名称：

  Design, Synthesis, Application, and DFT Investigation of Suzuki−Miyaura Reactions of a Dicobalt Carbonyl-Containing Phosphine Ligand

  摘要：

  The preparation and characterization of a novel dicobalt-containing monophosphine ligand, 4a, is presented. Palladium-catalyzed Suzuki-Miyuara reactions employing 4a/Pd(OAc)(2) were pursued. The optimized reaction conditions were found to start with 1 molar equiv of aryllialides, 1.5-fold of phenylbronic acid, 3-fold of KF in 1 mL of THF, and I mol % of 4a/Pd(OAc)2 as catalytic precursor. The P-31 NMR studies reveal moderate reductive capacity of 4a toward Pd(OAc)(2). The unique bonding mode of 4a toward Pd ensures that the ratio of 4a/Pd is equal to 1:1. Two plausible active species, I and [I-OAc](-), were proposed as the catalytically active species in the Suzuki-Miyaura cross-coupling reaction. The validity of this assumption was examined by P-31 NMR spectra and density functional theory (DFT) means. In addition, we have demonstrated theoretically that the dicobalt moiety of 4a acts as an effective auxiliary in stabilizing the Pd(0) center during catalytic reaction.

  DOI：

  10.1021/om050060j
• 作为产物：
  描述：

  二叔丁基氯化膦 、 苯乙炔 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 25.0h， 生成 (phenylethynyl)di-t-butylphosphine
  参考文献：
  名称：

  桥联芳乙炔基上具有吸电子/给电子取代基的含钴大体积单齿膦的制备及其在铃木偶联反应中的应用

  摘要：

  几个含钴笨重齿膦（μ-PPH 2 CH 2 PPH 2）有限公司2（CO）4（μ，η-（吨丁基）2 PCC（C 6 H ^ 4 R））（图4a：R = H; 4b中：R = p -F; 4cp：R = p -CF 3 ; 4cm：R = m -CF 3 ; 4d：R = p -OMe）由（t Bu）2 PCC（R–C 6）反应制得高4）（2a：R ＝ H；2b：R ＝p- F；2cp：R ＝p- CF 3； n ＝1。2cm：R ＝m -CF 3；m＝1。2D：R = p -OMe）用Co 2（CO）6（μ-PPH 2 CH 2 PPH 2）3。的进一步的反应图4a，图4b，4CP，4厘米，和4d中，用Pd（OAC）2，产生独特的钯络合物（μ-PPH 2 CH 2 PPH2）有限公司2（CO）4（μ，η-（吨丁基）2 PCC（C 6 H ^ 3 R）-κC 1）的Pd（μ-OAC）（图5a：R

  DOI：

  10.1016/j.tet.2008.04.117

文献信息

• A Convenient and Direct Route to Phosphinoalkynes via Copper-Catalyzed Cross-Coupling of Terminal Alkynes with Chlorophosphanes
  作者：Irina P. Beletskaya、Vladimir V. Afanasiev、Marina A. Kazankova、Irina V. Efimova、Mikhail U. Antipin

  DOI：10.1055/s-2003-42493

  日期：——

  A new efficient method to obtain various alkynylphosphanes RnP(-R′)3-n [R = Ar, Alk, alkoxy, amido R′ = Ar, Het, Alk, CH2Z (Z = OMe, NMe2), n = 0-2] has been developed by means of cross-coupling reaction of chlorophosphanes RnPCl3-n (R = Ar, Alk, Alkoxy) with terminal alkynes catalyzed by cuprous salts.

  一种新颖高效的方法已被开发，用于通过铜盐催化的氯膦化合物RnPCl3-n（R = Ar、Alk、烷氧基）与末端炔烃的交叉耦合反应获得各种炔基膦 RnP(-R′)3-n [R = Ar、Alk、烷氧基，R′ = Ar、Het、Alk、CH2Z（Z = OMe、NMe2），n = 0-2]。
• Phosphirenium borate betaines from alkynylphosphanes and the halogeno-B(C₆F₅)₂ reagents
  作者：Atsushi Ueno、Jennifer Möricke、Constantin G. Daniliuc、Gerald Kehr、Gerhard Erker

  DOI：10.1039/c8cc07189f

  日期：——

  of phosphanyl substituted alkynes R12P–CC–R2 [R12P: Mes2P or tBu2P; R2: SiMe3, Ph, tBu] reacts with the X–B(C6F5)2 reagents [X: Cl, Br] to give thermally rather stable neutral zwitterionic phosphirenium borate products. Five examples of this class of compounds were characterized by X-ray diffraction.

  一系列膦酰基取代的炔烃R 1 2 P– CC C–R 2 [R 1 2 P：Mes 2 P或t Bu 2 P；R 2：SiMe 3，Ph，t Bu]与X–B（C 6 F 5）2试剂[X：Cl，Br]反应，得到热稳定的中性两性离子硼酸磷鎓产物。此类化合物的五个实例通过X射线衍射表征。
• Some complexes of platinum, palladium, rhodium, and iridium formed from the bulky ligand (phenylethynyl)di-t-butylphosphine
  作者：H. David Empsall、Eileen M. Hyde、Eric Mentzer、Bernard L. Shaw

  DOI：10.1039/dt9770002285

  日期：——

  cis-[PtMe2L2] and trans-[PtCl(Me)L2] are prepared by displacing cyclo-octa-1,5-diene (cod) from [PtMe2(cod)], etc., but with 2 mol of L [PtCl2(cod)] readily gives [PtCl2(cod)L] in which only one of the cod double bonds is co-ordrnated. The complexes trans-[MCl(CO)L2](M = Rh or Ir) have also been prepared and the iridium complex converted into [IrHCl2(CO)L2] with HCl. With trans-[MCl(CO)L2] one rotamer is much

  新的磷化氢PBu t 2（C CPh）（L）给出反式-[MX 2 L 2 ]类型的配合物（M = Pd或PT，X = Cl或I），由于围绕磷的旋转受限而作为构象体存在–金属键。该配合物对亲核攻击具有很高的抵抗力，但是反式-[PTCl 2 L 2 ]可以被质子化，例如，在CF 3 CO 2 H中，[PTCl 2 L PBu t 2（CH CPh）}] +的形式可逆并很干。氯化氢[PTCl 2 PBu t 2 [CH获得C（Cl）Ph]} 2 ]。配合物的顺式- [PTME 2大号2 ]和反式- [氯铂酸（ME）L- 2 ]通过从移位环辛-1,5-二烯（COD）的制备[PTME 2（COD）]，等等。，但用2mol L [PTCl 2（cod）L ]容易得到[PTCl 2（cod）L]，其中只有一个鳕鱼双键被配位。还制备了反式-[MCl（CO）L 2 ]（M = Rh或Ir）的配合物，铱配合物用HCl转化为[IrHCl
• PNPCB heterocycles via thermal and Lewis acid catalyzed trans-hydroborations
  作者：Louie Fan、Douglas W. Stephan

  DOI：10.1039/c6dt01659f

  日期：——

  (R = Ph 5, tBu 6, Cy 7) were reacted to give the products tBu2P(CCR)NP(BH3)iPr2 (R = Ph 8, tBu 9, Cy 10) and Ph2P(CCR)NP(BH3)iPr2 (R = Ph 11, tBu 12, Cy 13). Subsequent thermally induced or Lewis acid catalyzed intramolecular hydroboration of 8 and 11 afforded the PNPCB heterocyclic compounds Ph2P(CCHPh)NP(BH2)iPr214 and tBu2P(CCHPh)NP(BH2)iPr215, respectively. Compounds 8–11 and 13–15 were crystallographically

  化合物iPr 2 P（BH 3）N 3 1，t Bu 2 PC CR（R = Ph 2，t Bu 3，Cy 4）和Ph 2 PC CR（R = Ph 5，t Bu 6，Cy 7）为反应得到产物t Bu 2 P（C CR）NP（BH 3）iPr 2（R = Ph 8，t Bu 9，Cy 10）和Ph 2 P（CCR）NP（BH 3）iPr 2（R = Ph 11，t Bu 12，Cy 13）。随后的热诱导或路易斯酸催化的8和11分子内氢硼化得到PNPCB杂环化合物Ph 2 P（C CHPh）NP（BH 2）iPr 2 14和t Bu 2 P（C CHPh）NP（BH 2）iPr 2 15， 分别。化合物8-11和13-15 进行了晶体学表征，并考虑了合成无机杂环的机理和意义。
• Oxygen insertion in a carbon–phosphorus bond of the phenylethynyl-di-(tert-butyl)-phosphine bridged dicobalt complex: exploring the nature of oxygen migration using DFT
  作者：Yi-Luen Huang、Chin-Pei Chang、Fung-E Hong

  DOI：10.1039/b611359a

  日期：——

  by spectroscopic means as well as the single-crystal X-ray diffraction method. This is the first crystallographic evidence that unambiguously supports the formation of an organometallic version of a phosphinate ester. The mechanism for the formation of 5 from 4a was proposed, and its validity was examined by DFT means. For the purpose of comparison, a similar mechanism illustrating the transformation

  在好氧条件下的分离过程中，苯乙炔基-二-（叔丁基）-膦桥联的二钴络合物[[micro-PPh（2）CH（2）PPh（2））Co2（CO）4（micro，eta-PhC [三键] CP（t-Bu）2）] 4a进行了部分氧化。氧化产物的身份[[micro-PPh（2）CH（2）PPh（2））Co2（CO）4（micro，eta-PhC [三键] COP（[双键] O）（t- Bu）2）] 5，是通过光谱方法以及单晶X射线衍射法确定的。这是第一个晶体学证据，明确支持形成次膦酸酯的有机金属形式。提出了由4a形成5的机理，并通过DFT手段对其有效性进行了检验。为了比较的目的，研究了类似的机理，该机理说明了PhC [三键] CP（t-Bu）2 1O转化为PhC [三键] COP（[双键] O]（t-Bu）2 5O（5的有机对应物）的过程。用同样的方法 已经发现，尽管效果很小，但金属碎片确实能够通过降低