(S)-(+)-hexane-1,3-diol | 108943-42-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (S)-(+)-hexane-1,3-diol
• 英文别名: (S)-(+)-1,3-hexanediol；(S)-hexane-1,3-diol；(3S)-hexane-1,3-diol
• CAS: 108943-42-6
• 化学式: C₆H₁₄O₂
• 分子量: 118.176
• InChiKey: AVIYEYCFMVPYST-LURJTMIESA-N

物化性质

• 沸点：
  228.2±8.0 °C(Predicted)
• 密度：
  0.961±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-(+)-hexane-1,3-diol 在 palladium on activated charcoal 三丁基膦 、 四丁基氟化铵 、 氢气 、 sodium hexamethyldisilazane 、 碳酸氢钠 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 三氟乙酸 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 95.5h， 生成 (E)-Oct-2-enoic acid (2S,3R,4aS,5S,8aR)-5-((S)-5-hydroxy-octyl)-2-methyl-decahydro-quinolin-3-yl ester
  参考文献：
  名称：

  Facile Entry to Substituted Decahydroquinoline Alkaloids. Total Synthesis of Lepadins A−E and H

  摘要：

  Condensation of a L-alanine derived delta-bromo-beta-silyloxy-propylamine with 1,3-cyclohexadione followed by alkylative cyclization produces a bicyclic enone. Diastereoselective Pt/C-catalyzed hydrogenation of this enone in HOAc provides a 5-oxo-cis-fused decahydroquinoline. Wittig olefination of this decahydroquinoline and subsequent epimerization of the resulting 5-formyl intermediate gives rise to a 5-beta-formyl decahydroquinoline exclusively. In a parallel procedure, Peterson reaction of this decahydroquinoline and subsequent hydrogenation of the generated 5-exo-olefin provides a decahydroquinoline with a 5-alpha-substituent predominantly. For these two diastereoselective processes, using the intermediates without N-protection as the substrates is essential because the corresponding N-Boc intermediates give poor diastereoselectivity. The intermediate with beta-form side chain is further converted into lepadins A-C via carbon chain elongation, while the intermediate with alpha-form side chain is transformed into lepadins D, E, and H and corresponding 5'-epimers via connection with two sulfones generated from two Sharpless epoxidation products. By comparison of the rotations and NMR data, the stereochemistry of lepadins D, E, and H is assigned as 2S, 3R, 4aS, 5S, 8aR, 5'R.

  DOI：

  10.1021/jo061070c
• 作为产物：
  描述：

  S-3-hydroxyhexanoic Acid methyl ester 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以68%的产率得到(S)-(+)-hexane-1,3-diol
  参考文献：
  名称：

  Enantioselective ruthenium-mediated synthesis of (-)-indolizidine 223AB

  摘要：

  Triphenylphosphine/CCl4-mediated cyclization of amino alcohol 17 proceeded smoothly, with single inversion, to provide (-)-indolizidine 223AB 4. Amino alcohol 17 was prepared by thermolysis of azide 16, followed by DIBAL reduction of the intermediate imine. Symchiral aldehyde 12 and phosphonium salt 15, precursors to 16, were prepared by BINAP.Ru*-mediated hydrogenation of the corresponding beta-keto esters. A simplified procedure allows this hydrogenation to be carried out in a Parr shaker, at 80-degrees-C and 50 psig of H-2.

  DOI：

  10.1021/jo00048a037

文献信息

• [1,3]-Transfer of Chirality during the Nicholas Reaction in γ-Benzyloxy Propargylic Alcohols
  作者：David D. Díaz、Miguel A. Ramírez、Víctor S. Martín

  DOI：10.1002/chem.200501127

  日期：2006.3.8

  gamma-acetylenic diols with BF3 x OEt2 provides bis-homopropargylic alcohols. The reaction occurs within seconds, tolerates a wide range of functionalities, and provides good yields. When the ether group is located at a stereochemically defined carbon atom, the rearrangement occurs with high stereoselectivity, transferring the chirality of the carbinol center to the newly created stereocenter. The cleavage

  描述了高度区域和立体选择性的分子内[1,5]-氢转移过程。用BF3 x OEt2处理γ-苄基保护的Co2（CO）6-α，γ-炔二醇可提供双均炔丙基醇。反应在几秒钟内发生，可耐受多种功能，并提供良好的收率。当醚基位于立体化学定义的碳原子上时，重排会以高立体选择性发生，从而将甲醇中心的手性转移至新创建的立体中心。当存在另外的苄基醚时，苄氧基的裂解是完全区域选择性的。评价了该新方法在密集取代的底物中的范围和局限性，还描述了可能的竞争反应和/或立体化学影响。
• A stereoselective total synthesis of (−)-andrachcinidine via an olefin cross-metathesis protocol
  作者：Palakodety Radha Krishna、G. Dayaker

  DOI：10.1016/j.tetlet.2007.08.053

  日期：2007.10

  A stereoselective total synthesis of 1-(2S,6R)-6-[(2S)-2-hydroxypentyl]-hexahydro-2-pyridinylacetone, (−)-andrachcinidine is reported. The strategy utilizes olefin cross-metathesis and intramolecular SN2 cyclization as the key steps.

  将1-立体选择性全合成（2小号，6 - [R）-6 - [（2-小号）-2-羟基戊基] -六氢-2- pyridinylacetone，（ - ） -报道andrachcinidine。该策略利用烯烃交叉复分解和分子内S N 2环化作为关键步骤。
• Brønsted acid promoted intramolecular cyclization of <i>O</i>-alkynyl benzoic acids: Concise total synthesis of exserolide F
  作者：Mohan Dumpala、Lingaswamy Kadari、Palakodety Radha Krishna

  DOI：10.1080/00397911.2018.1491994

  日期：2018.9.17

  Abstract Herein we report the stereoselective total synthesis of Exserolide F. The key step involves triflic acid catalyzed highly regioselective intramolecular cyclization of an O-alkynyl benzoic acid derivative to accomplish the core isocoumarin skeleton of the natural product via 6-endo-dig mode of cyclization. The other important steps are: Sharpless asymmetric epoxidation, Barbier propargylation

  摘要 在此我们报告了 Exserolide F 的立体选择性全合成。关键步骤涉及三氟甲磺酸催化的 O-炔基苯甲酸衍生物的高度区域选择性分子内环化，通过 6-endo-dig 环化模式完成天然产物的核心异香豆素骨架. 其他重要步骤是：Sharpless 不对称环氧化、Barbier 炔丙基化、Sonogashira 偶联，以获取 O-炔基苯甲酸衍生物。图形概要
• Total Synthesis and Biological Evaluation of (+)-Neopeltolide and Its Analogues
  作者：Haruhiko Fuwa、Asami Saito、Shinya Naito、Keiichi Konoki、Mari Yotsu-Yamashita、Makoto Sasaki

  DOI：10.1002/chem.200901675

  日期：2009.11.23

  The stereocontrolled total synthesis of the originally proposed (1) and correct (2) structures of (+)‐neopeltolide, a novel marine macrolide natural product with highly potent antiproliferative activity against several cancer cell lines as well as potent antifungal activity, has been achieved by exploiting a newly developed Suzuki–Miyaura coupling/ring‐closing metathesis strategy. Alkylborate 44, which

  已实现了最初提出的（1）和正确的（2）结构（+）-新去甲内酯的立体控制全合成，这是一种新型海洋大环内酯类天然产物，对多种癌细胞系具有高度有效的抗增殖活性，并且具有较强的抗真菌活性通过开发新开发的Suzuki-Miyaura耦合/闭合环置换策略。由碘化物34原位生成的烷基硼酸酯44通过Suzuki-Miyaura偶联剂与磷酸烯醇酯8偶联。衍生二烯45的闭环易位，然后进行立体选择性氢化，得到四氢吡喃47作为单一立体异构体，从34的高总收率。我们的战略融合，使我们构建的14元大环内酯核心结构2在一个快速和有效的方式。全合成的和合成的中间体和设计的合成类似物的生物学评价，进行建立的结构-活性关系2，导致结构上简单而有效的细胞毒性类似物的发现，9-demethylneopeltolide（54）。
• First stereoselective total synthesis of phomonol via oxa-Michael approach
  作者：Palakodety Radha Krishna、Sunchu Prabhakar

  DOI：10.1016/j.tetlet.2013.05.018

  日期：2013.7

  Herein we report the first stereoselective total synthesis of phomonol via Sharpless asymmetric dihydroxylation and 6-exo-trig oxa-Michael addition as the key steps.

  本文中，我们报告了通过Sharpless不对称二羟基化反应和6 - exo -trig oxa-Michael加成反应首次合成立体选择性的膦酰基酚的关键步骤。