trans-2-(diphenylphosphanyl)cyclohexan-1-ol | 154781-55-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-2-(diphenylphosphanyl)cyclohexan-1-ol
• 英文别名: trans-2-(diphenylphosphino)cyclohexanol；(1R,2R)-2-diphenylphosphanylcyclohexan-1-ol
• CAS: 154781-55-2
• 化学式: C₁₈H₂₁OP
• 分子量: 284.338
• InChiKey: GQHRWOLYFCDDBA-QZTJIDSGSA-N

物化性质

• 沸点：
  416.4±38.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  trans-2-(diphenylphosphanyl)cyclohexan-1-ol 在 吡啶 、 正丁基锂 、 三氯硅烷 、 双氧水 、 sulfur 作用下， 以 四氢呋喃 为溶剂， 反应 19.5h， 生成 (1S,2R)-2-(Diphenyl-phosphinothioyl)-cyclohexanol
  参考文献：
  名称：

  β Effect of Phosphorus Functionalities

  摘要：

  Diphelnylphosphinoyl (-P(=O)Ph(2)) and diphenylthiophosphinoyl (-P(=S)Ph(2)) respectively are modest and strong p-effect functionalities. When these groups are antiperiplanar to mesylate, the substrates solvolyze through unimolecular ionization. In contrast, substrates with the synclinal (gauche) arrangement react bimolecularly with solvent. The anti/gauche rate ratio is 440 for the oxide and 3.2 x 10(6) for the sulfide at 25 degrees C. The antiperiplanar sulfide in fact reacts 220 times more rapidly than the analogous cyclohexyl substrate at 25 degrees C, despite the strong electron-withdrawing nature of diphenylthiophosphinoyl. The a-secondary hydrogen/deuterium kinetic isotope effects of 1.21 for the anti oxide and 1.26 for the anti sulfide suggest kigh sp(2) character in the transition state, as expected for stabilization by hyperconjugation in a vertical mechanism. Energies calculated at the MP2 level show that the geometry with the P-C bond parallel to the empty carbocation p orbital is more stable than the perpendicular geometry by 22.94 kcal mol(-1) for PH2, 8.80 kcal mol(-1) for P(O)H-2, and 10.54 kcal mol(-1) for P(S)H-2, confirming significant hyperconjugation for these substituents. The global minimum, however, is the bridged structure (four-membered rings for the oxide and sulfide, three-membered ring for the simple phosphine), so that the mechanistic choice between a vertical mechanism (hyperconjugation) and a nonvertical mechanism (bridging) is not clear-cut.

  DOI：

  10.1021/ja9537181
• 作为产物：
  描述：

  氧化环己烯 、 二苯基膦 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以33%的产率得到trans-2-(diphenylphosphanyl)cyclohexan-1-ol
  参考文献：
  名称：

  用于代谢靶向和顺序生物正交标记的环丙烯酮

  摘要：

  环丙烯酮是生物正交化学的有吸引力的基序，因为它们的尺寸小和独特的反应模式。不幸的是，反应最快的环丙烯酮对于常规细胞内使用来说不够稳定。在这里，我们报告了稳定性提高的环丙烯酮，可与生物正交膦保持稳健的反应性。合成了功能化的环丙烯酮，并分析了它们在水介质和细胞环境中的寿命。用一组膦探针进一步处理最稳定的环丙烯酮，并测量反应速率。与之前报道的试剂相比，两种膦支架提供了约 100 倍的速率增强。重要的是，稳定的环丙烯酮适用于通过遗传密码扩展生产重组蛋白。

  DOI：

  10.1021/jacs.7b03010

文献信息

• A Simple Building‐Block Route to (Phosphanyl‐carbene)palladium Complexes via Intermolecular Addition of Functionalised Phosphanes to Isocyanides
  作者：Michael R. Eberhard、Bart van Vliet、Laura Durán Páchon、Gadi Rothenberg、Graham Eastham、Huub Kooijman、Anthony L. Spek、Cornelis J. Elsevier

  DOI：10.1002/ejic.200801067

  日期：2009.4

  (phosphanyl-carbene)PdII complexes. These complexes have bidentate ligands containing an acyclic diamino- or aminooxy-carbene and a phosphane. The synthesis gives good yields (typically 70-90 %) for a variety of complexes (22 compounds). Moreover, it does not require the synthesis of imidazolium salts nor the a priori generation of free carbenes. Three of the new complexes were tested as catalysts

  我们提出了一个简单的协议来制造 (phosphanyl-carbene)PdII 复合物。这些配合物具有包含无环二氨基-或氨基氧基-卡宾和磷烷的双齿配体。该合成为各种复合物（22 种化合物）提供了良好的产率（通常为 70-90%）。此外，它不需要合成咪唑鎓盐，也不需要预先生成游离卡宾。三种新配合物被测试作为 Sonogashira 和 Hay 偶联反应的催化剂，具有良好的产率和选择性。
• A Cyclopropenethione-Phosphine Ligation for Rapid Biomolecule Labeling
  作者：R. David Row、Jennifer A. Prescher

  DOI：10.1021/acs.orglett.8b02296

  日期：2018.9.21

  Cyclopropenethiones are reported as new bioorthogonal reagents. These motifs react readily with substituted phosphines to provide thiocarbonyl adducts. In some cases, the ligations are >300-fold faster than analogous reactions with bioorthogonal cyclopropenones. Dialkyl cyclopropenethiones are also stable in aqueous buffers and can be used for biomolecule labeling in vitro and in cell lysate. The rapid

  据报道，环丙烯硫酮是新的生物正交试剂。这些基序易于与取代的膦反应以提供硫代羰基加合物。在某些情况下，连接比与生物正交环丙烯酮的类似反应快300倍以上。二烷基环丙烯硫酮在水性缓冲液中也很稳定，可用于体外和细胞裂解液中的生物分子标记。环丙烯硫酮的快速反应性和生物相容性表明，它们将是细胞研究的有用探针。
• An Approach to the Synthesis of Platinum Complexes Containing Chiral Monodentate Phosphines with Simultaneous Regeneration of the Resolving Agent
  作者：Joan Albert、Jaume Granell、Jorge Mínguez、Guillermo Muller、Daniel Sainz、Pedro Valerga

  DOI：10.1021/om970176i

  日期：1997.7.1

  Elution of compounds [PdCl3-ClC6H3CHNCH(Me)Ph}trans-2-PPh2(CyOH)}] 5a and [PdXC6H4CH(Me)NH2}Ph2PCH(OMe)Ph}] 6b, containing the racemic phosphines as ligands, through a SiO2 column allows the separation of the two diastereoisomers. Optically active coordination complexes trans-[PtCl2Ph2PCH(OMe)Ph}2] and trans-[PtCl2Ph2PCH(OMe)Ph}(PPh3)], have been obtained by ligand transfer reactions between

  化合物[PdCl 3-ClC 6 H 3 CH NCH（Me）Ph} 反式2-PPh 2（CyOH）}] 5a和[PdX C 6 H 4 CH（Me）NH 2 } Ph 2的洗脱含有外消旋膦作为配体的PCH（OMe）Ph}] 6b通过SiO 2色谱柱可以分离两种非对映异构体。光学活性配位化合物反式-[PtCl 2 Ph 2 PCH（OMe）Ph} 2 ]和反式-[PtCl 2 Ph 2 PCH（OMe）Ph}（PPh 3）]分别通过6b与PtCl 2或反式[PtCl（μ-Cl）（PPh 3）] 2之间的配体转移反应获得。可以从铂化合物中分离出双核环palpalated拆分剂，并将其用于新的拆分过程中。
• Ligands with cycloalkane backbones II. Chelate ligands from 2-(diphenylphosphinyl) cyclohexanol: Syntheses and transition metal complexes
  作者：Catherine L. Thurner、Michael Barz、Michael Spiegler、Werner R. Thiel

  DOI：10.1016/s0022-328x(97)00013-2

  日期：1997.8

  1 and 3 with chlorodiphenyl phosphine led to new chiral bidentate ligands, bearing a phosphinite donor fragment. Several new transition metal complexes of these ligands were characterized spectroscopically and by X-ray structure analysis.

  从PPh 3（Ph = C 6 H 5），锂金属和环氧环己烷开始，通过一锅法反应以约80％的产率获得（±）-2-（二苯基膦基）环己醇（1）。膦部分的氧化。与元素硫或与过氧化氢。得到相应的硫化膦3。氧化物2。后者形成固态的二聚体。1和3的OH片段与氯二苯基膦的反应生成新的手性双齿配体，带有次膦酸酯供体片段。这些配体的几种新的过渡金属配合物通过光谱和X-射线结构分析进行了表征。
• Synthesis of monohydroxy -methyl- and -ethyl-phosphines PPh2CHROH
  作者：Guillermo Muller、Daniel Sainz

  DOI：10.1016/0022-328x(95)05425-o

  日期：1995.6

  The preparation of alpha-hydroxyphosphines PPh(2)CHROH with R = H (a), Ph (b) and Et (c), and beta-hydroxyphosphines PPh(2)CHR'HROH (e-i) has been achieved in high yield by reaction of HPPh(2) or LiPPh(2) with RCHO or the oxides of cyclohexene (e), limonene (f), styrene (g, h) and pinene (i). With the exception of styrene oxide, the reactions with the oxides are very regioselective, giving only one of the possible isomers. Cis- and trans-limonene oxides react with LiPPh(2) in different conditions selectively, giving trans-phosphino derivatives from commercial mixtures of limonene oxide.