methyl 2,2‐diphenylpent‐4‐ynoate | 906542-82-3

• 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: methyl 2,2‐diphenylpent‐4‐ynoate
• 英文别名: methyl 2,2-diphenyl-4-pentynoate；methyl 2,2-diphenylpent-4-ynoate
• CAS: 906542-82-3
• 化学式: C₁₈H₁₆O₂
• 分子量: 264.324
• InChiKey: PPNAIPJUOJEKHK-UHFFFAOYSA-N

物化性质

• 沸点：
  394.4±30.0 °C(Predicted)
• 密度：
  1.103±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  methyl 2,2‐diphenylpent‐4‐ynoate 在 氯[2-(二叔丁基磷)二苯基]金 、 silver(I) 4-methylbenzenesulfonate lithium aluminium tetrahydride 、 二异丙胺 、 copper(I) bromide 作用下， 以 1,4-二氧六环 、 乙醚 、 甲苯 为溶剂， 反应 16.05h， 生成 4,4-diphenyl-2-vinyltetrahydrofuran
  参考文献：
  名称：

  用于与碳、氮和氧亲核试剂对艾伦烯进行分子内外加氢官能化的高活性 Au(I) 催化剂

  摘要：

  (2,2-二苯基-4,5-己二烯基)氨基甲酸苄酯 (4) 与 Au[P(t-Bu)2(o-biphenyl)]Cl (2) 和 AgOTf 的 1:1 催化混合物反应5 mol%) 在二恶烷中在 25 摄氏度下 45 分钟导致 4,4-二苯基-2-乙烯基吡咯烷-1-羧酸苄酯 (5) 的分离，产率为 95%。Au(I) 催化的 N-烯丙氨基甲酸酯的分子内加氢胺化耐受烷基和烯基碳原子处的取代，并且对于哌啶衍生物的形成是有效的。γ-羟基和δ-羟基丙二烯也在室温下几分钟内经历了金催化的分子内加氢烷氧基化，以高产率和高外选择性形成相应的氧杂环。2-烯基吲哚在室温下几分钟内经历金催化的分子内加氢芳基化，以良好的产率形成4-乙烯基四氢咔唑。

  DOI：

  10.1021/ja062045r
• 作为产物：
  描述：

  二苯基乙酸甲酯 、 3-溴丙炔 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 2,2‐diphenylpent‐4‐ynoate
  参考文献：
  名称：

  远程合作组策略使配体能够促进不对称金催化

  摘要：

  通过手性配体金属的配合，首次实现了加速性不对称金催化。设计的手性联萘基配体中不对称定位的远端酰胺基团起一般碱催化剂的重要作用，并选择性地促进4-allen-1-ols环化成一个前手性异戊烯面。该反应大多数是与非手性底物高度对映选择性的，并且由于催化的加速性质，允许低至100ppm的负载。在任何主链sp 3上都存在一个预先存在的手性中心碳-碳，该反应保持高效，最重要的是，无论底物的立体化学如何，都能保持出色的异戊烯表面选择性。通过使用配体和底物对映体的不同组合，现在可以以极高的选择性获得通用的2-乙烯基四氢呋喃的所有四种立体异构体。该化学的基础设计揭示了一种新颖的，概念上独特的策略来应对具有挑战性的不对称金催化，迄今为止，该策略依赖于减速性不对称空间位阻方法。

  DOI：

  10.1021/jacs.7b09136

文献信息

• Leveraging the Micellar Effect: Gold-Catalyzed Dehydrative Cyclizations in Water at Room Temperature
  作者：Stefan R. K. Minkler、Nicholas A. Isley、Daniel J. Lippincott、Norbert Krause、Bruce H. Lipshutz

  DOI：10.1021/ol403402h

  日期：2014.2.7

  The first examples of gold-catalyzed cyclizations of diols and triols to the corresponding hetero- or spirocycles in an aqueous medium are presented. These reactions take place within nanomicelles, where the hydrophobic effect is operating, thereby driving the dehydrations, notwithstanding the surrounding water. By the addition of simple salts such as sodium chloride, reaction times and catalyst loadings

  介绍了在水介质中金催化的二醇和三醇环化成相应杂环或螺环的第一个例子。这些反应发生在纳米胶束内，疏水作用在其中起作用，从而推动脱水，尽管周围有水。通过添加简单的盐，例如氯化钠，可以显着减少反应时间和催化剂负载。
• Unusual regiodivergence in metal-catalysed intramolecular cyclisation of γ-allenols
  作者：Jannine L. Arbour、Henry S. Rzepa、Andrew J. P. White、King Kuok (Mimi) Hii

  DOI：10.1039/b913295c

  日期：——

  Different O-heterocycles can be obtained from a common γ-allenol precursor by using Ag, Zn or Sncatalysts; the results were rationalised by molecular modelling.

  不同种类的O-杂环可以通过使用银、锌或锡催化剂从一种共同的γ-烯醇前体中获得，并且通过分子模拟对结果进行了合理化解释。
• Synthesis of Multisubstituted 2-(Dihydrofuran-2(3H)-ylidene)acetates via Intramolecular Carboalkoxylation by Platinum−Olefin Catalyst System
  作者：Itaru Nakamura、Ching Siew Chan、Toshiharu Araki、Masahiro Terada、Yoshinori Yamamoto

  DOI：10.1021/ol702795u

  日期：2008.1.1

  The cyclization of 6-(1-alkoxyethyl)hex-2-ynoates in the presence of a platinum-olefin catalyst system gave the corresponding multisubstituted 2-(dihydrofuran-2(3H)-ylidene)acetates in good to high yields. The Z/E selectivity is controlled by the electronic property of the ester group; the 2,2,2-trichloroethyl ester led to the Z isomer, while the phenyl ester gave the E isomer.
• Stereochemical Control by an Ester Group or Olefin Ligand in Platinum-Catalyzed Carboalkoxylation of 6-(1-Alkoxyethoxy)- hex-2-ynoates
  作者：Itaru Nakamura、Ching Siew Chan、Toshiharu Araki、Masahiro Terada、Yoshinori Yamamoto

  DOI：10.1002/adsc.200800772

  日期：2009.5

  Abstractmagnified imageThe cyclization of 6‐(1‐alkoxyethoxy)hex‐2‐ynoantes in the presence of the platinum‐olefin catalyst system gave the corresponding multisubstituted 2‐[dihydrofuran‐2(3H)‐ylidene]acetates in good to high yields. The Z/E selectivity is controlled by the electronic property of the ester group; the 2,2,2‐trichloroethyl ester yielded the Z isomer, while the phenyl ester gave the E isomer. Moreover, we found that the Z/E selectivities in the reaction of phenyl esters 1h, 1n, and 1o were controlled by the olefin ligand. For example, the platinum‐catalyzed reaction of 1h using 1,5‐hexadiene as the olefin ligand gave E‐2h as the major product, while that using 1,5‐cyclooctadiene produced mainly the Z isomer.
• Mechanism of the Platinum(II)-Catalyzed Hydroamination of 4-Pentenylamines
  作者：Christopher F. Bender、Timothy J. Brown、Ross A. Widenhoefer

  DOI：10.1021/acs.organomet.5b00821

  日期：2016.1.25

  The mechanism of the platinum(II)-catalyzed intramolecular hydroamination of benzyl 4-pentenylamines has been evaluated under stoichiometric and catalytic conditions. Reaction of a benzyl 2,2-disubstituted 4-pentenylamine with [(PPh3)Pt(mu-COCl](2) forms a thermally sensitive platinum amine complex that undergoes irreversible, intramolecular ligand exchange with the pendant C=C bond to form a reactive platinum pi-alkene complex. The pi-alkene complex undergoes rapid, outer-sphere C-N bond formation, evidenced by the anti addition of Pt and N across the complexed C=C bond, to form a thermally stable zwitterionic platinamethylpyrrolidinium complex. The zwitterionic complex is rapidly and exergonically deprotonated by free amine to form a neutral, bicyclic azaplatinacyclobutane complex that likely exists as a discrete 1:1 adduct with ammonium salt in the nonpolar reaction medium and that represents the resting state of the catalytic cycle. Turnover-limiting intramolecular protodemetalation of the azaplatinacyclobutane ammonium adduct followed by ligand exchange releases the 2-methylpyrrolidine product.