cis-2-(4-chlorophenyl)-4-hydroxy-tetrahydropyran

• 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: cis-2-(4-chlorophenyl)-4-hydroxy-tetrahydropyran
• 英文别名: (2R,4S)-2-(4-chlorophenyl)oxan-4-ol
• 化学式: C₁₁H₁₃ClO₂
• 分子量: 212.676
• InChiKey: SMDAPVBKEBEABV-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (+/-)-2-(4-chlorophenyl)-tetrahydro-2H-pyran-4-one 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以64 %的产率得到cis-2-(4-chlorophenyl)-4-hydroxy-tetrahydropyran
  参考文献：
  名称：

  3-Bromobut-3-en-1-ols 和醛的 Prins 环化非对映选择性合成 2,6-二取代四氢吡喃酮

  摘要：

  四氢吡喃酮由 3-bromobut-3-en-1-ols 和醛合成，产率高，在 -35 °C 下具有出色的非对映选择性。该反应首先形成最稳定的六元椅状四氢吡喃基碳阳离子，然后对羟基进行亲核攻击，随后消除 HBr 得到四氢吡喃酮。使用 Wittig 反应将四氢吡喃酮的羰基部分转化为烯醇醚和酯。它也被氢化铝锂以高达 96% 的非对映选择性转化为具有 2,4- 和 4,6-顺式构型的 4-羟基-2,6- 二取代四氢吡喃。此外，该方法还扩展到新型抗癌氨基胍化合物的合成。

  DOI：

  10.1021/acs.joc.2c02715

文献信息

• Enantioselective Reduction of Prochiral Ketones Employing Sprouted Pisum sativa as Biocatalyst
  作者：Jhillu Yadav、Basi Reddy、Chittamuru Sreelakshmi、Adari Rao

  DOI：10.1055/s-0028-1088047

  日期：2009.6

  Sprouted green peas have been used for the first time as biocatalysts for enantioselective reduction of prochiral ketones. The reactions are highly enantioselective to furnish chiral alcohols in good yields. The sprouted peas as biocatalysts are a cheap and easy way for generating some interesting chiral alcohols. This process is efficient and convenient to produce chiral secondary alcohols in water.

  发芽的青豆首次被用作生物催化剂，用于手性选择性还原前手性酮。这些反应具有高度手性选择性，可高产率地生成手性醇。发芽青豆作为生物催化剂是一种廉价且简便的方法，用于生成一些有趣的手性醇。该过程在水相中高效、方便地制备手性仲醇。
• Bismuth triflate catalyzed prins-type cyclization in ionic liquid: Synthesis of 4-tetrahydropyranol derivatives
  作者：M. S. R. Murty、K. Rajasekhar、V. Harikrishna、J. S. Yadav

  DOI：10.1002/hc.20403

  日期：2008.1

  The reaction of aldehydes with homoallylic alcohols in the presence of catalytic amount of bismuth triflate in [bmim]PF6generates 4-tetrahydropyranol derivatives in excellent yield and with high diastereoselectivity. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:104–106, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20403

  在催化量的 [bmim] PF6 中的三氟甲磺酸铋存在下，醛与高烯丙醇的反应以优异的收率和高非对映选择性生成 4-四氢吡喃醇衍生物。© 2008 Wiley Periodicals, Inc. 杂原子化学 19:104–106, 2008; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20403
• Enzymatic kinetic resolution of racemic 4-tetrahydropyranols by Candida rugosa lipase
  作者：J.S. Yadav、B.V.Subba Reddy、B. Padmavani、Ch. Venugopal、A.Bhaskar Rao

  DOI：10.1016/j.tetlet.2007.04.091

  日期：2007.6

  Enzymatic kinetic resolution of (±)-hydroxytetrahydropyrans has been achieved for the first time by means of lipase-mediated transesterification to afford optically active (2S,4R)-tetrahydropyranyl acetates and (2R,4S)-tetrahydropyranols in excellent yields with high enantioselectivity. Absolute configurations of the tetrahydropyranyl acetates were assigned as (S) by chemical correlation.

  （±）-羟基四氢吡喃的酶促动力学拆分首次通过脂肪酶介导的酯交换反应实现，从而以优异的产率提供了光学活性的（2 S，4 R）-四氢吡喃乙酸酯和（2 R，4 S）-四氢吡喃酚具有高对映选择性。通过化学相关性将乙酸四氢吡喃酯的绝对构型指定为（S）。
• The ‘Aqueous’ Prins Cyclization: A Diastereoselective Synthesis of 4-Hydroxytetrahydropyran Derivatives
  作者：Jhillu Yadav、Basi Subba Reddy、Gunda Narayana Kumar、Seema Aravind

  DOI：10.1055/s-2007-1000932

  日期：2008.2

  Phosphomolybdic acid (H3PMo12O40, a heteropoly acid) is found to catalyze efficiently the Prins cyclization of homoallylic alcohols with aldehydes in water at room temperature to provide tetrahydropyran-4-ol derivatives in high yields with all cis-selectivity. Only cyclic ketones can give spirocyclic products. The use of phosphomolybdic acid in water makes this procedure simple, more convenient, cost-effective, and environmentally friendly.

  研究发现，磷钼酸（H3PMo12O40，一种杂多酸）可在室温下高效催化同源烯丙基醇与醛在水中的普林斯环化反应，以高产率和全顺选择性提供四氢吡喃-4-醇衍生物。只有环酮才能生成螺环产物。在水中使用磷钼酸使这一过程变得简单、方便、经济和环保。
• Diastereoselective Synthesis of 2,4-Disubstituted Tetrahydropyranols and Ethers via a Prins-Type Cyclization Catalyzed by Scandium Triflate
  作者：Wen-Chun Zhang、Chao-Jun Li

  DOI：10.1016/s0040-4020(00)00152-6

  日期：2000.4

  The reaction of aldehydes with homoallylic alcohols catalyzed by scandium triflate gives rise to the formation of 2-substituted tetrahydropyran-4-ols and ethers in good overall yields and with ‘all-cis’ configurations and high diastereoselectivities. The stereochemistries of these products were assigned with the assistance of coupling constants and NOE. Factors affecting the reaction have been examined

  醛与三氟甲磺酸scan催化的均丙醇反应生成了2-取代的四氢吡喃-4-醇和醚，总收率高，具有“顺式”构型和高非对映选择性。这些产物的立体化学在偶合常数和NOE的帮助下进行分配。已经详细研究了影响反应的因素。发现该反应在氯仿中最有效。各种芳香族和脂肪族醛均顺利进行环化。已经提出了用于该反应的催化循环。