(4S,6S)-4-Hydroxy-6-(benzyloxy)-1-heptene | 136521-65-8

• 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: (4S,6S)-4-Hydroxy-6-(benzyloxy)-1-heptene
• 英文别名: (4S,6S)-6-(benzyloxy)hept-1-en-4-ol；(4S,6S)-6-phenylmethoxyhept-1-en-4-ol
• CAS: 136521-65-8
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: UCBRUQGFKILSTQ-JSGCOSHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  (4S,6S)-4-Hydroxy-6-(benzyloxy)-1-heptene 在 氨 、 lithium 、 potassium hydride 作用下， 反应 5.33h， 生成 (4S,6S)-4-(methoxy)-6-hydroxy-1-heptene
  参考文献：
  名称：

  Synthetic Studies toward the Total Synthesis of Swinholide. 1. Stereoselective Construction of the C₁₉−C₃₅ Subunit

  摘要：

  The development of an approach directed at the total synthesis of the complex cytotoxic marine macrodiolide swinholide is described. The present study focuses on the development of a synthetic route far the preparation of the C-19-C-35 segment of the structure, which is composed of a trisubstituted pyran moiety with a contrathermodynamic anti arrangement of the C-2 and C-6 pyran substituents (swinholide C-27 and C-31) which is joined by an ethano linker to an acyclic array containing five contiguous stereocenters. The pyran subunit was constructed using a stereoselective allylation of a beta-alkoxy aldehyde with 1,3-asymmetric induction and a second stereoselective allylation to prepare the C-glycosidic type of linkage. Use of the Hafner-Duthaler reagent was investigated as a potential means of constructing the anti vicinal hydroxyl-methyl relationships found in the C-19-C-24 Segment but was found not to be practical in this instance. The Evans bis propionate methodology was used to introduce a four-carbon unit, and a Mukaiyama aldol was used for chain extension to incorporate the remaining two carbons and two stereocenters of this segment. Attempted use of the Hanessian benzylidene acetal fragmentation reaction in this sequence was thwarted by neighboring group participation of an oxazolidinone in one case and an unexpected regiochemical outcome in another. The approach developed affords the C19-C35 substructure in 18 steps overall from ethyl acetoacetate and in adequate quantities (10% overall yield) to support the projected total synthesis.

  DOI：

  10.1021/jo990291y
• 作为产物：
  描述：

  2,2,2-三氯乙酰胺苄酯 在 四氯化钛 、 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 (4S,6S)-4-Hydroxy-6-(benzyloxy)-1-heptene
  参考文献：
  名称：

  Synthetic Studies toward the Total Synthesis of Swinholide. 1. Stereoselective Construction of the C₁₉−C₃₅ Subunit

  摘要：

  The development of an approach directed at the total synthesis of the complex cytotoxic marine macrodiolide swinholide is described. The present study focuses on the development of a synthetic route far the preparation of the C-19-C-35 segment of the structure, which is composed of a trisubstituted pyran moiety with a contrathermodynamic anti arrangement of the C-2 and C-6 pyran substituents (swinholide C-27 and C-31) which is joined by an ethano linker to an acyclic array containing five contiguous stereocenters. The pyran subunit was constructed using a stereoselective allylation of a beta-alkoxy aldehyde with 1,3-asymmetric induction and a second stereoselective allylation to prepare the C-glycosidic type of linkage. Use of the Hafner-Duthaler reagent was investigated as a potential means of constructing the anti vicinal hydroxyl-methyl relationships found in the C-19-C-24 Segment but was found not to be practical in this instance. The Evans bis propionate methodology was used to introduce a four-carbon unit, and a Mukaiyama aldol was used for chain extension to incorporate the remaining two carbons and two stereocenters of this segment. Attempted use of the Hanessian benzylidene acetal fragmentation reaction in this sequence was thwarted by neighboring group participation of an oxazolidinone in one case and an unexpected regiochemical outcome in another. The approach developed affords the C19-C35 substructure in 18 steps overall from ethyl acetoacetate and in adequate quantities (10% overall yield) to support the projected total synthesis.

  DOI：

  10.1021/jo990291y

文献信息

• A Unified Synthetic Approach to Optically Pure Curvularin-Type Metabolites
  作者：Srinivasa Rao Allu、Sreenivas Banne、Jia Jiang、Na Qi、Jian Guo、Yun He

  DOI：10.1021/acs.joc.9b00776

  日期：2019.6.7

  A unified and concise approach to the synthesis of nine curvularin-type metabolites and two analogues has been developed with few steps and high yields. Among them, sumalactones A–D were synthesized for the first time. The key steps in this approach included esterification, Friedel–Crafts acylation, and ring-closing metathesis (or cross metathesis).

  已经开发出了一种统一，简洁的方法来合成九种卡维拉林型代谢物和两种类似物，且步骤少且产率高。其中，舒马内酯A–D是首次合成。该方法的关键步骤包括酯化，Friedel-Crafts酰化和闭环易位（或交叉易位）。
• Total Synthesis of Tetraketide and Cryptorigidifoliol I via a Sequential Allylation Strategy
  作者：Birakishore Padhi、G. Sudhakar Reddy、Debendra K. Mohapatra

  DOI：10.1021/acs.jnatprod.6b00443

  日期：2016.11.23

  cryptorigidifoliol I (2) has been devised successfully from commercially available starting materials in 11 and 17 steps, with 16% and 11% overall yields, respectively. Highlights of the syntheses involved sequential Lewis acid-catalyzed highly regio- and diastereoselective allylations and intramolecular Mitsunobu lactonization.

  已经从商业上可得的起始原料成功地为11步和17步设计了统一的高效合成四酮化合物（1）和隐秘三氟酚I（2）的合成路线，总收率分别为16％和11％。合成的亮点涉及连续的路易斯酸催化的高度区域和非对映选择性的烯丙基化和分子内光延内酯化。
• First stereoselective total synthesis of an anti-fouling agent, C2-symmetric natural macrolide trichobotryside A
  作者：Siva Ganesh Narala、G. Nagalatha、A. Venkat Narsaiah

  DOI：10.24820/ark.5550190.p010.795

  日期：——

  A stereoselective total synthesis of 16-membered macrodiolide trichobotryside A has been accomplished. The key features are: regioselective epoxide opening, Reetz anti-allylation, Sharpless asymmetric epoxidation, cross metathesis and Yamaguchi protocols for esterification followed by macrolactonization.

  已完成 16 元大环二内酯 trichobotryside A 的立体选择性全合成。主要特征是：区域选择性环氧化物开环、Reetz 反烯丙基化、Sharpless 不对称环氧化、交叉复分解和 Yamaguchi 协议，用于酯化，然后是大环内酯化。
• Concerning the role of Lewis acids in chelation controlled addition to chiral alkoxy aldehydes
  作者：M.T. Reetz、K. Kesseler、A. Jung

  DOI：10.1016/s0040-4039(01)80011-3

  日期：1984.1

  Chiral α- and β-alkoxy aldehydes react stereoselectively with various C-nucleophiles in the presence of Lewis acids to provide chelation controlled adducts.

  在路易斯酸存在下，手性α-和β-烷氧基醛与各种C-亲核试剂立体选择性反应，以提供螯合控制的加合物。
• 1,3-Asymmetric induction in addition reactions of chiral .beta.-alkoxy aldehydes: efficient chelation control via Lewis acidic titanium reagents
  作者：M. T. Reetz、A. Jung

  DOI：10.1021/ja00352a051

  日期：1983.7