2,5-cis-2-(1-hydroxy-1-methylethyl)-5-phenyltetrahydrofuran | 128797-92-2

• 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: 2,5-cis-2-(1-hydroxy-1-methylethyl)-5-phenyltetrahydrofuran
• 英文别名: cis-2-(1-hydroxy-1-methylethyl)-5-phenyltetrahydrofuran；cis-5-Phenyl-2-(2-hydroxy-2-propyl)tetrahydrofuran；cis-2-(5-phenyltetrahydrofuran-2-yl)-propan-2-ol；cis-2-(5-phenyltetrahydrofuran-2-yl)propan-2-ol；cis-2-(tetrahydrofuran-2-yl)-2-propanol；2-[(2S,5R)-5-phenyloxolan-2-yl]propan-2-ol
• CAS: 128797-92-2；128798-02-7
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: DLHOSOFLOOXHRD-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,5-cis-2-(1-hydroxy-1-methylethyl)-5-phenyltetrahydrofuran 在 VOL₁(OEt)(EtOH) 叔丁基过氧化氢 作用下， 以 氯仿 为溶剂， 反应 168.0h， 以18%的产率得到3-benzoyloxy-2,2-dimethyl-5-γ-butyrolactone
  参考文献：
  名称：

  （席夫碱）钒（V）络合物催化氧化取代双（高烯丙基）醇 - 官能化四氢呋喃的立体选择性合成

  摘要：

  钒 (V) 配合物 4 已由三齿席夫碱配体 3 和 VO(OEt)3 制备。对所有钒 (V) 化合物进行了表征（IR、UV/Vis 和 51V NMR 光谱，在选定的实施例中通过 X 射线衍射分析）并用作氧化催化剂，用于从取代的双 ( homoallylic) 醇 1（单或三取代的 C-C 双键）。在优化条件下氧化仲或叔 1-烷基-、1-乙烯基-或 1-苯基取代的 5,5-二甲基-4-戊烯-1-醇 [TBHP 作为主要氧化剂和 1,2-(氨基)茚满醇衍生的钒（V）试剂 4g 作为催化剂]以合成有用的产率和非对映选择性（22-96% de）提供了 2,5-顺式配置的四氢呋喃。另一方面，从 2- 或 3- 烷基-和 2- 或 3-苯基-取代的 5,5-二甲基-4-戊烯-1-醇双（高烯丙）醇的氧化获得反式二取代的氧杂环戊烷 (62%−96 de) . 用 TBHP 和催化量的钒 (V) 配合物 4g

  DOI：

  10.1002/ejoc.200200644
• 作为产物：
  描述：

  Benzoic acid 5-methyl-1-phenyl-hex-4-enyl ester 在 二氯二茂钛 叔丁基过氧化氢 、 sodium hydroxide 、 4 A molecular sieve 作用下， 以 甲醇 、 癸烷 、 二氯甲烷 为溶剂， 反应 22.0h， 生成 2,5-cis-2-(1-hydroxy-1-methylethyl)-5-phenyltetrahydrofuran
  参考文献：
  名称：

  Diastereoselective Titanocene-Catalyzed Oxidative Cyclization of Bishomoallylic Alcohols

  摘要：

  Bishomo醇在Cp2TiCl2/t-丁基过氧化氢/活化的4 Å分子筛体系中以良好的产率和立体选择性转化为四氢呋喃醇和四氢吡喃醇。

  DOI：

  10.1055/s-2001-16779

文献信息

• Activation of molecular oxygen and its use in stereoselective tetrahydrofuran-syntheses from δ,ε-unsaturated alcohols
  作者：Bárbara Menéndez Pérez、Dominik Schuch、Jens Hartung

  DOI：10.1039/b804588g

  日期：——

  2-propanol at 60 degrees C. Ring closures occurred diastereoselectively and afforded 2,3-trans- (96% de), 2,4-cis- (approximately 60% de), and 2,5-trans-substituted (>99% de) (phenyl)tetrahydrofur-2-ylmethanols as major components. Formation of bicyclic compounds and a 2,3,4,5-substituted oxolane was feasible as exemplified by syntheses of oxabicyclo[4.3.0]nonylmethanols and a derivative of natural product

  如果用O（2）和bis 2,2,2-三氟甲基-1-[（1R，4S）-1,7,7处理-三甲基-2-（氧代-κ）双环[2.2.1]庚-3-基]乙醇基-}钴（ii）在2-丙醇溶液中在60摄氏度下发生。非对映选择性发生闭环反应，得到2,3 -反-（96％de），2,4-顺-（约60％de）和2,5-反-取代（> 99％de）（苯基）四氢呋喃-2-基甲醇为主要成分。双环化合物和2,3,4,5-取代的环氧丙烷的形成是可行的，例如在61-72％（de-90-99％）中合成了oxabicyclo [4.3.0]壬基甲醇和天然产物厚朴素的衍生物。四氢呋喃合成的有效性主要取决于（i）溶剂，（ii）反应温度，（iii）初始钴浓度，（iv）羟基和乙烯基之间的链长，和（v）在反应实体上的取代。提出了用于合理化观察到的选择性的序列。
• cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes as catalysts for oxidative alkenol cyclization by tert-butyl hydroperoxide
  作者：Maike Dönges、Matthias Amberg、Georg Stapf、Harald Kelm、Uwe Bergsträßer、Jens Hartung

  DOI：10.1016/j.ica.2014.02.007

  日期：2014.8

  cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes are Lewis acids able to catalyze oxidative cyclization of alkenols by tert-butyl hydroperoxide (TBHP). Terminal dimethyl-substituted (prenyl-type) 4-pentenols bearing an alkyl or a phenyl group in position 1 afford under such conditions 2,5-cis-derivatives of 2-(tetrahydrofuran-2-yl)-2-propanol as major and tetrahydropyran-3-ols as minor products (four examples). Oxidizing 1-phenyl-6-methylhept-5-en-l-ol yields a 75125-mixture of the derived 2-(tetrahydropyran-2-yl)-2-propanol and an oxepan-3-ol, whereas 2-propenols give epoxides in up to 94% yield. Epoxidizing geraniol by TBHP in the presence of a vanadium catalyst prepared from (2,5,6R)-2-diphenylmethanol-6-hydroxymethylpiperidine occurs enantioselectively. Highfield shifts of vanadium-51 resonances upon adding alkyl hydroperoxides to solutions of cis-2,6-bis-(methanolate)-piperidine vanadium(V) complexes point to vanadium(V) tert-butyl peroxy complex formation as key step for activating peroxides. (C) 2014 Elsevier B.V. All rights reserved.
• Formation of 3-acyloxy-γ-butyrolactones from 4-pentenols in vanadium-catalyzed oxidations
  作者：Matthias Amberg、Maike Dönges、Georg Stapf、Jens Hartung

  DOI：10.1016/j.tet.2014.05.011

  日期：2014.8

  O-Acyl derivatives of 3-hydroxy-gamma-butyrolactone are formed in up to 20% yield as by-products from 1-alkyl- and 1-phenyl-substituted 4-pentenols and tert-butyl hydroperoxide (TBHP) in vanadium-catalyzed synthesis of (tetrahydrofuran-2-yl)-methanols. The lactones are secondary products formed from (tetrahydrofuran-2-yl)-methanols via hydrogen atom abstraction in positions 4 and 5, as derived from experiments starting from deuterium-labeled alkenols. Stereocenters at tetrahydrofuran carbon 2 and the proximate hydroxyl carbon of the alkanol side chain retain configuration in the course of oxidative tetrahydrofuran conversion. In an atmosphere of nitrogen or argon, no gamma-butyrolactone formation occurs, pointing to dioxygen as terminal oxidant for the secondary oxidation. Adding cyclohexa-1,4-diene or gamma-terpinene to a solution of a 4-pentenol, TBHP, and a vanadium catalyst exposed to air inhibits formation of gamma-butyrolactones. A third approach to prevent gamma-butyrolactones from being formed in oxidative 4-pentenol cyclization uses cis-2,6-bis-(methanol)-piperidine instead of N-salicylidene-ortho-aminophenol as tridentate auxiliary for the vanadium catalyst. (C) 2014 Elsevier Ltd. All rights reserved.
• Hartung, Jens; Schmidt, Philipp, Synlett, 2000, # 3, p. 367 - 370
  作者：Hartung, Jens、Schmidt, Philipp

  DOI：——

  日期：——
• Heterocyclisations induced by thallium(III) acetate. Effect of varying the internal nucleophile
  作者：Joseph P. Michael、Mluleki M. Nkwelo

  DOI：10.1016/s0040-4020(01)82035-4

  日期：1990.1