4-甲基四氢吡喃-1-醇 | 10444-28-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 中文名称: 4-甲基四氢吡喃-1-醇
• 英文名称: 4-methyltetrahydropyran-1-ol
• 英文别名: 5-methyltetrahydropyran-2-ol；5-hydroxy-4-methyl-pentanal cyclohemiacetal；5-methyl-tetrahydro-pyran-2-ol；5-Methyloxan-2-ol
• CAS: 10444-28-7
• 化学式: C₆H₁₂O₂
• 分子量: 116.16
• InChiKey: XYTJEQXHDFWATK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  4-甲基四氢吡喃-1-醇 在 四丙基高钌酸铵 、 4 A molecular sieve 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以81%的产率得到5-甲基四氢吡喃-2-酮
  参考文献：
  名称：

  烷氧基取代基在六元环二氧碳鎓离子中采用电子优选伪轴取向的结构证据

  摘要：

  当 C-4 处存在远程烷基或烷氧基取代基时，单取代四氢吡喃缩醛的亲核取代反应会产生相反的选择性。结合早期关于糖基化反应中间体的计算报告，这些结果与衍生自烷氧基取代的四氢吡喃缩醛的氧代碳鎓离子中间体占据假轴构象的偏好一致。提供了类似且更稳定的二氧碳鎓离子中这种构象偏好的理论、光谱和 X 射线晶体学证据。

  DOI：

  10.1021/ja050830i
• 作为产物：
  描述：

  5,6-二氢-6-甲氧基-2H-吡喃-3(4H)-酮 在 Wilkinson's catalyst 盐酸 、 正丁基锂 作用下， 以 四氢呋喃 、 甲苯 、 正戊烷 为溶剂， -78.0~23.0 ℃ 、689.49 kPa 条件下， 反应 66.0h， 生成 4-甲基四氢吡喃-1-醇
  参考文献：
  名称：

  取决于取代基的亲核取代反应的立体化学逆转：杂原子取代的六元环氧碳鎓离子通过假轴构象体的反应

  摘要：

  DOI：

  10.1021/ja993366o

文献信息

• Structural Evidence that Alkoxy Substituents Adopt Electronically Preferred Pseudoaxial Orientations in Six-Membered Ring Dioxocarbenium Ions
  作者：Stephen Chamberland、Joseph W. Ziller、K. A. Woerpel

  DOI：10.1021/ja050830i

  日期：2005.4.1

  pseudoaxial conformation. Theoretical, spectroscopic, and X-ray crystallographic evidence of this conformational preference in an analogous and more stable dioxocarbenium ion are provided. This contrasteric preference for an axial orientation of an alkoxy substituent likely derives from the electronically favored pseudoaxial orientation of remote electronegative substituents in neutral six-membered rings

  当 C-4 处存在远程烷基或烷氧基取代基时，单取代四氢吡喃缩醛的亲核取代反应会产生相反的选择性。结合早期关于糖基化反应中间体的计算报告，这些结果与衍生自烷氧基取代的四氢吡喃缩醛的氧代碳鎓离子中间体占据假轴构象的偏好一致。提供了类似且更稳定的二氧碳鎓离子中这种构象偏好的理论、光谱和 X 射线晶体学证据。
• Redox Reorganization: Aluminium Promoted 1,5‐Hydride Shifts Allow the Controlled Synthesis of Multisubstituted Cyclohexenes
  作者：Lewis B. Smith、Roly J. Armstrong、Jingyan Hou、Edward Smith、Ming Sze、Alistair J. Sterling、Alex Smith、Fernanda Duarte、Timothy J. Donohoe

  DOI：10.1002/anie.202307424

  日期：2023.9.4

  An efficient synthesis of cyclohexenes has been achieved from easily accessible tetrahydropyrans via a tandem 1,5‐hydride shift–aldol condensation. We discovered that readily available aluminium reagents, e.g. Al₂O₃ or Al(O^tBu)₃ are essential for this process, promoting the 1,5‐hydride shift with complete regio‐ and enantiospecificity (in stark contrast to results obtained under basic conditions). The mild conditions, coupled with multiple methods available to access the tetrahydropyran starting materials makes this a versatile method with exceptional functional group tolerance. A wide range of cyclohexenes (>40 examples) have been prepared, many in enantiopure form, showing our ability to selectively install a substituent at each position around the newly forged cyclohexene ring. Experimental and computational studies revealed that aluminium serves a dual role in facilitating the hydride shift, activating both the alkoxide nucleophile and the electrophilic carbonyl group.

  摘要 通过串联 1,5-酸酐转移-醛醇缩合，从容易获得的四氢吡喃中高效合成了环己烯。我们发现，铝试剂（如 Al2O3 或 Al(OtBu)3）在这一过程中非常重要，可促进 1,5-酸酐转移，并具有完全的区域特异性和对映体特异性（与在碱性条件下获得的结果形成鲜明对比）。温和的条件加上多种获得四氢吡喃起始材料的方法，使该方法成为一种具有特殊官能团耐受性的多功能方法。我们已经制备出了多种环己烯（40 个实例），其中许多是对映体，这表明我们有能力在新形成的环己烯环周围的每个位置选择性地安装一个取代基。实验和计算研究表明，铝在促进氢化物转移方面起着双重作用，既能激活亲氧化烷基的亲核体，又能激活亲电羰基。
• Method for manufacturing aminoalcohol
  申请人：Kuraray Co., Ltd., Kurashiki Plant

  公开号：EP1074541A1

  公开（公告）日：2001-02-07

  An aminoalcohol is synthesized by reacting a cyclic hemiacetal expressed by Formula 1 (where n is 0 or 1; R1 and R2 are each a hydrogen atom, a monovalent saturated hydrocarbon group which is optionally substituted, or a monovalent aromatic group which is optionally substituted, or R1 and R2 are bonded together into a divalent saturated hydrocarbon group which is optionally substituted; and R3, R4, and R5 are each a hydrogen atom, a monovalent saturated hydrocarbon group which is optionally substituted, or a monovalent aromatic group which is optionally substituted), with hydrogen and any one of ammonia, a primary amine and secondary amine in the presence of a hydrogenation catalyst.

  氨基乙醇是由式 1 所表示的环状半缩醛通过反应合成的 (其中 n 为 0 或 1；R1 和 R2 各为氢原子、任选被取代的一价饱和烃基或任选被取代的一价芳香基，或 R1 和 R2 键合为任选被取代的二价饱和烃基；以及 R3、R4 和 R5 各为氢原子、任选被取代的一价饱和烃基或任选被取代的一价芳香基）、 在氢化催化剂存在下，与氢和氨、伯胺和仲胺中的任一种反应。
• CYCLIC HEMIACETAL COMPOUND PRODUCTION METHOD
  申请人：Kuraray Co., Ltd.

  公开号：EP3822261A1

  公开（公告）日：2021-05-19

  Provided is a method for producing a specific hemiacetal compound, the method including reacting a specific alcohol having an unsaturated bond, carbon monoxide, and hydrogen in the presence of a compound of Group 8 to Group 10 transition metal, a tertiary phosphite ligand, and a base, wherein an A value represented by the equation (1) is 0.0 to 4.0, and a B value represented by the equation (2) is 0.6 to 1.0.

  本发明提供了一种生产特定半缩醛化合物的方法，该方法包括使具有不饱和键的特定醇、一氧化碳和氢在第 8 族至第 10 族过渡金属化合物、叔亚磷酸酯配体和碱的存在下反应，其中式（1）表示的 A 值为 0.0 至 4.0，式（2）表示的 B 值为 0.6 至 1.0。
• Diastereoselective Synthesis of Cycloalkylamines by Samarium Diiodide-Promoted Cyclizations of α-Amino Radicals Derived from α-Benzotriazolylalkenylamines
  作者：José M. Aurrecoechea、Beatriz López、Alvaro Fernández、Ana Arrieta、Fernando P. Cossío

  DOI：10.1021/jo960957d

  日期：1997.2.1

  The condensation of omega-unsaturated aldehydes with benzotriazole and secondary amines affords alpha-benzotriazolylalkenylamines that exist in solution as mixtures of the corresponding benzotriazol-1-yl and benzotriazol-2-yl isomers resulting from their rapid dissociation into iminium cations and the benzotriazolyl anion. The reduction of these adducts with samarium diiodide (SmI2) takes place with formation of the benzotriazolyl anion and alpha-amino alkenyl radicals that undergo 5- or 6-exo-trig cyclizations leading to substituted cycloalkyl- or cycloheteroalkylamines. The presence of an electron-withdrawing substituent in the alkene subunit is required for efficient cyclizations. The formation of cyclopentylamines takes place with unusually high 1,5-cis selectivity (hex-5-enyl radical numbering), and the presence of a 2- or 4-Me substituent also imparts high 1,2- or 1,4-trans stereoinduction, respectively. The corresponding six-membered rings, however, are formed with low diastereoselectivity. Semiempirical calculations performed on model systems suggest that a stabilizing secondary orbital interaction between the amino group and the electron-deficient alkene might in part account for the enhanced cis-selectivity encountered.