4-(tetrahydropyranyl-2-oxy)-4-methyl-2-pentanone | 57283-21-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 4-(tetrahydropyranyl-2-oxy)-4-methyl-2-pentanone
• 英文别名: 2-Pentanone, 4-methyl-4-[(tetrahydro-2H-pyran-2-yl)oxy]-；4-methyl-4-(oxan-2-yloxy)pentan-2-one
• CAS: 57283-21-3
• 化学式: C₁₁H₂₀O₃
• 分子量: 200.278
• InChiKey: UGCJZXMZVGOCRT-UHFFFAOYSA-N

物化性质

• 沸点：
  85-90 °C(Press: 0.5 Torr)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(tetrahydropyranyl-2-oxy)-4-methyl-2-pentanone 在 poly-p-styryl-acetonyltriphenylphosphonium bromide 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以74%的产率得到二丙酮醇
  参考文献：
  名称：

  乙酰基三苯基溴化phosph及其聚合物支撑的类似物作为醇作为烷基乙烯基醚的保护和脱保护催化剂

  摘要：

  乙炔基三苯基溴化（（ATPB，1）和聚对苯乙烯基二苯基乙yl基溴化（（A）都是有效的催化剂，可保护醇（如THP，THF和EE醚）以及将THP，THF和EE醚裂解为相应的醇酒精。它们可用于1°，2°和3°的醇，苯酚和酸不稳定的醇。在本研究中，ATPB和催化剂A都是极好的催化剂。它仅需要1×10 -2 –1.25×10 -2 摩尔当量。反应中聚合物负载的催化剂A的量。

  DOI：

  10.1016/s0040-4020(01)00558-0
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 二丙酮醇 在 N_.N'-bis[3,5-bis(trifluoromethyl)phenyl]thiourea 作用下， 反应 18.0h， 以98%的产率得到4-(tetrahydropyranyl-2-oxy)-4-methyl-2-pentanone
  参考文献：
  名称：

  Generally Applicable Organocatalytic Tetrahydropyranylation of Hydroxy Functionalities with Very Low Catalyst Loading

  摘要：

  本文介绍了首个无酸、有机催化的四氢吡喃和2-甲氧基丙烯对醇、酚及其他ROH衍生物的保护方法，利用了特权的N,N'-双[3,5-双(三氟甲基)苯基]硫脲及其聚苯乙烯结合类似物。这些反应广泛适用于（包括制备规模）对酸敏感的底物，如醛醇产物、羟基酯、缩醛、硅烷保护的醇和氰醇。催化效率非常高，转化数达到10万，转化频率高达每小时5700次，催化剂负载量低至0.001 mol%。通过计算支持的机理解释强调了氢键辅助的醇异裂和过渡态中氧阴离子穴的优先稳定。

  DOI：

  10.1055/s-2007-965917

文献信息

• Lithium Hexafluorophosphate-Catalyzed Efficient Tetrahydropyranylation of Tertiary Alcohols under Mild Reaction Conditions
  作者：Tsuneo Sato、Nao Hamada

  DOI：10.1055/s-2004-829550

  日期：——

  Lithium hexafluorophosphate is found to be an efficient catalyst for the tetrahydropyranylation of tertiary alcohols with dihydropyran under mild reaction conditions.

  在温和的反应条件下，六氟磷酸锂被发现是叔醇与二氢吡喃的四氢吡喃化反应的有效催化剂。
• Synthese totale de la (±) bisabolangelone (1)
  作者：Bernard Riss、Bernard Muckensturm

  DOI：10.1016/s0040-4020(01)80090-9

  日期：1989.1

  Bisabolangelone is a sesquiterpenoid well known for its strong antifeeding properties against phytophagous insects. In this communication, we describe the total synthesis of the target molecule, following a model study, wich shows the possibilities to cyclizise γ-acetylenic alcohols, in view to obtain 2-(2-alkenylidene)-tetrahydrofurans, an essential moiety of bisabolangelone.

  Bisabolangelone是一种倍半萜类化合物，以其对食草性昆虫的强抗食性而闻名。在此交流中，我们通过模型研究描述了目标分子的总合成，这表明环化γ-炔醇的可能性，以期获得2-（2-亚链烯基）-四氢呋喃，这是双硼苯醌的基本组成部分。
• Total synthesis of (±)-bisabolangelone
  作者：Bernard P Riss、Bernard Muckensturm

  DOI：10.1016/s0040-4039(00)85112-6

  日期：1986.1

  The total synthesis of the sesquiterpenoid (±) bisabolangelone is described. The key step utilizes the heterocyclic five membered ring formation by cyclisation of a γ-acetylenic alcohol with the formation of an exocyclic conjugated enol ether in high yield.

  描述了倍半萜（±）双硼苯醌的总合成。关键步骤是通过γ-炔醇的环化利用杂环五元环的形成，并以高收率形成环外共轭烯醇醚。
• Stereochemical and Mechanistic Studies on Conjugate Addition of Organocuprates to Acyclic Enones and Enoates:  Simple Rule for Diastereofacial Selectivity
  作者：Keiko Yamamoto、Hiroshi Ogura、Jun-ichi Jukuta、Hiroko Inoue、Kazuhiro Hamada、Youko Sugiyama、Sachiko Yamada

  DOI：10.1021/jo980308x

  日期：1998.6.1

  Systematic studies of organocuprate conjugate additions to three pairs of gamma-epimeric and geometrically isomeric gamma-chiral acyclic enones (1a, 2a; 1b, 2b; and 3, 4) and two pairs of gamma-chiral acyclic enoates (5, 6 and 7, 8) allowed us to generalize diastereofacial selectivity of these reactions. The diastereoselectivity depended on the double-bond geometry, the configuration at the gamma-position, and the reaction conditions. In reactions without activating additives, cuprate added to the si-face of the geometrically isomeric pair of E- and Z-enones (1a and 2a) with high diastereoselectivity (98%), while their epimers at the gamma-position (3 and 4) yielded re-facial adduct preferentially (86-97%). Addition of TMSC1 and HMPA together not only accelerated the addition reaction but also completely changed the pattern of pi-facial selectivity. In reactions containing those additives, cuprates added to isomeric E- and Z-enones with reverse facial selectivity: E-enone la gave the si-facial adduct exclusively, whereas isomeric Z-enone 2a yielded the re-facial adduct with high selectivity(97%). Their gamma-epimers gave opposite results; namely, the E-isomer 3 reacted with re-facial selectivity (97%), while the Z-isomer 4 reacted with si-facial selectivity (75%).;Under conditions where both TMSC1 and HMPA were present, even the enoates (5-8) reacted efficiently with similarly reverse and high facial selectivity. On the basis of these results, we postulate a general and clear-cut rule to predict diastereofacial selectivity of cuprate conjugate additions in which a possibility of Z-E isomerization of starting enones is taken into account as a crucial determinant.
• PFLIEGER, D.;MUCKENSTURM, B., TETRAHEDRON, 45,(1989) N, C. 2031-2040
  作者：PFLIEGER, D.、MUCKENSTURM, B.

  DOI：——

  日期：——