(R)-4,4-dimethyl-1-phenylpent-1-yn-3-ol | 132350-97-1

• 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: (R)-4,4-dimethyl-1-phenylpent-1-yn-3-ol
• 英文别名: (3R)-4,4-dimethyl-1-phenylpent-1-yn-3-ol
• CAS: 132350-97-1
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: FGMAZQOESWZPBV-LBPRGKRZSA-N

物化性质

• 沸点：
  287.6±23.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  (R)-4,4-dimethyl-1-phenylpent-1-yn-3-ol 在 三乙基硅烷 、 三氟甲磺酸三甲基硅酯 、 偶氮二甲酸二异丙酯 、 水 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 (3R,5S)-3-(tert-butyl)-5-phenyl-2-tosylisoxazolidine
  参考文献：
  名称：

  路易斯酸催化的炔丙基 N-羟基胺的还原性烷氧基化反应可立体选择性地获得异恶唑烷

  摘要：

  路易斯酸催化的炔丙基N-羟胺上的 5-内切-二元还原加氢烷氧基化级联反应可以方便、立体选择性地获得异恶唑烷衍生物。所开发的方法为异恶唑烷的合成提供了一种新方法，异恶唑烷是一种具有生物学优势的支架。通过合成 1,3-氨基醇、4-氨基四氢吡喃和 sedamine 天然产物，证明了所开发方法的合成潜力。

  DOI：

  10.1021/acs.orglett.3c00690
• 作为产物：
  描述：

  4,4-dimethyl-1-phenyl-1-pentyn-3-one 在 DIPCl 作用下， 以 乙醚 为溶剂， 反应 144.0h， 以80%的产率得到(R)-4,4-dimethyl-1-phenylpent-1-yn-3-ol
  参考文献：
  名称：

  Chiral synthesis via organoboranes. 34. Selective reductions. 47. Asymmetric reduction of hindered .alpha.,.beta.-acetylenic ketones with B-chlorodiisopinocampheylborane to propargylic alcohols of very high enantiomeric excess. Improved workup procedure for the isolation of product alcohols

  摘要：

  The Midland reagent, Alpine-Borane (2a), is excellent for the asymmetric reduction of many acetylenic ketones, but it fails with hindered derivatives. On the other hand, B-chlorodiisopinocampheylborane (DIP-Chloride, 4) reacts with hindered alpha,beta-acetylenic ketones to provide the corresponding propargylic alcohols in 96 to greater-than-or-equal-to 99% ee. The reaction is in accordance with the tentative mechanism proposed earlier. While 4-phenyl-3-butyn-2-one is reduced in only 21% ee, 4 reduces 4-methyl-1-phenyl-1-pentyn-3-one in 53% ee and 4,4-dimethyl-1-phenyl-1-pentyn-3-one in greater-than-or-equal-to 99% ee. The generality of this observation is demonstrated by reducing a series of hindered acetylenic ketones with increasing steric requirements and differing electronic environments. Thus, 2,2-dimethyl-4-tridecyn-3-one, 1-cyclopentyl-4,4-dimethyl-1-pentyn-3-one, and 3,3-dimethyl-5-tetradecyn-4-one are all reduced to the corresponding alcohols in greater-than-or-equal-to 99% ee and 97% ee, respectively. A modified and operationally simpler workup procedure for obtaining the alcohols in high isolated yields is described. Comparison of reagent 4 with 2a is also made, making clear the range of applicability of each reagent. This development makes it possible to reduce asymmetrically any acetylenic ketone by a judicious choice of either 2a or 4.

  DOI：

  10.1021/jo00034a034

文献信息

• Synthesis of new β-hydroxy amide ligands and their Ti(IV) complex-catalyzed enantioselective alkynylation of aliphatic and vinyl aldehydes
  作者：Ya-Min Li、Yi-Quan Tang、Xin-Ping Hui、Lu-Ning Huang、Peng-Fei Xu

  DOI：10.1016/j.tet.2009.03.005

  日期：2009.5

  new chiral β-hydroxy amide ligands were synthesized via the reaction of benzyl chloride and amino alcohols derived from l-tyrosine. The titanium(IV) complex of chiral ligand 8b was found to be an effective catalyst for the asymmetric alkynylation of aliphatic, vinyl and aromatic aldehydes. The propargyl alcohols were obtained in highly enantiomeric excesses (up to 96% ee) under optimized conditions.

  通过苄基氯与衍生自1-酪氨酸的氨基醇的反应，合成了三个新的手性β-羟基酰胺配体。发现手性配体8b的钛（IV）配合物是脂族，乙烯基和芳族醛的不对称烷基化的有效催化剂。在优化条件下以高度对映体过量（最高达96％ee）获得炔丙醇。
• Enantioselective Alkynylation of Aromatic Aldehydes: Pyridyl Phenylene Terpeneol Catalysts with Flexible Biaryl Axes
  作者：Bernd Goldfuss、Matthias Leven、David Müller

  DOI：10.1055/s-0030-1260325

  日期：2011.10

  Free rotating biaryl axes of pyridyl phenylene terpenols are fixed by zinc cations to give conformationally pure zinc complexes. These zinc alkoxide catalysts provide yields up to 99% and ee values up to 86% in the enantioselective addition of phenylacetylene to aromatic aldehydes. enantioselectivity - biaryls - organometallic reagents - zinc - alkynes

  吡啶基亚苯基萜烯醇的自由旋转的联芳基轴被锌阳离子固定，得到构象纯的锌络合物。在对芳香醛中苯乙炔的对映选择性加成中，这些烷氧基锌催化剂可提供高达99％的收率和ee值的高达86％。 对映选择性-联芳基-有机金属试剂-锌-炔烃
• Camphor-based Schiff base ligand SBAIB: an enantioselective catalyst for addition of phenylacetylene to aldehydes
  作者：Ramalingam Boobalan、Chinpiao Chen、Gene-Hsian Lee

  DOI：10.1039/c1ob06683h

  日期：——

  series of Schiff base ligands were synthesized from (1R)-camphor. Under the optimal conditions, (+)-SBAIB-a, 10 was found to be an excellent catalyst for the enantioselective addition of phenylacetylene to various aldehydes without utilizing either achiral additives or Ti(OiPr)4. This approach yielded (R)-propargylic alcohols in extremely high yields (up to 99%) and excellent enantioselectivities (up to

  从中合成了一系列席夫碱配体 （1 R）-樟脑。在最佳条件下（+）-SBAIB-a，10被发现是用于对映选择性加成的极好的催化剂苯乙炔 无需使用非手性添加剂或 钛（O i Pr）4。该方法以极高的产率（高达99％）和优异的对映选择性（高达92％）产生了（R）-丙炔醇。相应的（S）-丙炔醇的合成具有良好的对映选择性（高达91％）和极好的收率（高达99％），使用（-）-SBAIB-a，41岁。
• Cationic Rhodium(I)/Bisphosphane Complex-Catalyzed Isomerization of Secondary Propargylic Alcohols to α,β-Enones
  作者：Ken Tanaka、Takeaki Shoji、Masao Hirano

  DOI：10.1002/ejoc.200700071

  日期：2007.6

  alcohols to α,β-enones. A kinetic resolution of secondary propargylic alcohols proceeded with moderate selectivity with [Rh((R)-BINAP)]OTf as a catalyst. Mechanistic studies revealed that the isomerization proceeds through intramolecular 1,3- and 1,2-hydrogen migration pathways. The isomerization of propargylic diol derivatives was also investigated, which revealed that 1,4-diketones, furans, and α,β-enones

  我们已经确定氢化阳离子 Rh(I)/双膦配合物是用于将仲炔醇异构化为 α,β-烯酮的高活性催化剂。仲炔醇的动力学拆分以 [Rh((R)-BINAP)]OTf 作为催化剂以中等选择性进行。机理研究表明，异构化通过分子内 1,3- 和 1,2- 氢迁移途径进行。还研究了炔二醇衍生物的异构化，结果表明 1,4-二酮、呋喃和 α,β-烯酮是从 2-butyn-1,4-diol、1-methoxy-2-butyn-4- ol 和 1-acetoxy-2-butyn-4-ol 衍生物，分别。此外，研究了炔二醇异构化的化学选择性，并观察到炔丙基羟基的优先氧化。
• Mild and Expedient Asymmetric Reductions of α,β-Unsaturated Alkenyl and Alkynyl Ketones by TarB-NO₂ and Mechanistic Investigations of Ketone Reduction
  作者：Scott Eagon、Cassandra DeLieto、William J. McDonald、Dustin Haddenham、Jaime Saavedra、Jinsoo Kim、Bakthan Singaram

  DOI：10.1021/jo101530f

  日期：2010.11.19

  yields up to 99%. In the case of α,β-unsaturated alkenyl ketones, α-substituted cycloalkenones were reduced with up to 99% ee, while more substituted and acyclic derivatives exhibited lower induction. For α,β-ynones, it was found that highly branched aliphatic ynones were reduced with optimal induction up to 90% ee, while reduction of aromatic and linear aliphatic derivatives resulted in more modest enantioselectivity

  据报道，制备对映体纯度高的手性烯丙基和炔丙基醇的方法轻而易举。在最佳条件下，TarB-NO 2和NaBH 4在25°C下于1 h内将炔基和烯基酮还原，生成对映体过量的手性炔丙基和烯丙基醇，收率高达99％。在α，β-不饱和烯基酮的情况下，α-取代的环烯酮的还原度最高可达99％ee，而更多被取代和无环的衍生物则显示出较低的诱导率。对于α，β-炔酮，发现高支化的脂族炔酮在最高达90％ee的情况下以最佳诱导被还原，而芳族和线性脂族衍生物的还原导致更适度的对映选择性。使用（升源自（l）-酒石酸的）-TarB-NO 2试剂，我们通常获得具有（R）构型的高度对映体富集的手性烯丙基和炔丙基醇。由于先前的模型和饱和类似物预测的（S）构型的炔丙基产物的减少，因此进行了一系列新的机理研究，以确定过渡态芳族，烯基和炔基酮的可能取向。