(4R*,5R*,1'R*)-Tetrahydro-5-(1-hydroxy-3-phenylpropyl)-4,5-dimethyl-2-furanone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (4R*,5R*,1'R*)-Tetrahydro-5-(1-hydroxy-3-phenylpropyl)-4,5-dimethyl-2-furanone
• 英文别名: (3R*,4R*,5R*)-3,4-Dimethyl-5-hydroxy-7-phenyl-4-heptanolide；(4S,5S)-5-[(1S)-1-hydroxy-3-phenylpropyl]-4,5-dimethyloxolan-2-one
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: FSNPYZIVIBMUBD-WHOFXGATSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4R*,5R*,1'R*)-Tetrahydro-5-(1-hydroxy-3-phenylpropyl)-4,5-dimethyl-2-furanone 在 lithium aluminium tetrahydride 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 36.0h， 生成 (4R*,5R*,1'R*)-5-(3-Hydroxy-1-methylpropyl)-5-methyl-2-phenyl-4-(2-phenylethyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  Hydroxyl-Directed Intermolecular Ketone-Olefin Couplings Promoted by SmI2

  摘要：

  SmI2-promoted intermolecular ketone-olefin couplings are facilitated and stereocontrolled by hydroxyl groups incorporated within the starting materials. For example, the SmI2-induced ketone - olefin coupling reactions of alpha-hydroxy ketone 5 with ethyl acrylate, acrylonitrile, ethyl crotonate, and 2(5 H)-furanone proceeded with high stereocontrol to afford the syn-1,2-diol products 6-9 in good yields. Excellent diastereoselectivity was achieved in the reductive couplings of beta-hydroxy aldehyde 21 and erythro-beta-hydroxy ketone 24 with acrylonitrile using SmI2, to produce the anti-1,3-diols 22 and 25 in good yields. The sense of the stereo-selectivity was in full accord with a chelation-control model. In the proposed model, the stereochemistry of the reaction product is explained by assuming that a cyclic ketyl radical is generated during the initial single-electron reduction by SmI2. This radical species results from the chelation of the Sm-III cation, attached to the ketyl radical, with the hydroxyl group.

  DOI：

  10.1002/(sici)1521-3765(19991105)5:11<3252::aid-chem3252>3.0.co;2-d
• 作为产物：
  描述：

  (+/-)-1-(2-Phenylethyl)-3-propynyl acetate 在 samarium diiodide 、 sodium tetrachloroaurate(III) 、 水 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 为溶剂， 反应 0.08h， 生成 (4R*,5R*,1'R*)-Tetrahydro-5-(1-hydroxy-3-phenylpropyl)-4,5-dimethyl-2-furanone
  参考文献：
  名称：

  Samarium(II) Iodide Promoted Intermolecular Ketone-Olefin Couplings Chelation-Controlled by .alpha.-Hydroxyl Groups

  摘要：

  The hydroxyl group directed intermolecular ketone-olefin coupling reactions induced by SmI2 between alpha-hydroxyl ketones and alpha,beta-unsaturated esters occurred with excellent stereochemical control about the newly formed asymmetric centers.

  DOI：

  10.1021/jo00102a010

文献信息

• Urethane group directed reductive couplings mediated by SmI2
  作者：Fuyuhiko Matsuda、Motoi Kawatsura、Fumiko Dekura、Haruhisa Shirahama

  DOI：10.1039/a901791g

  日期：——

  coupling reactions of α-(alkoxycarbonyl)amino ketones 1 and 3 with methyl, ethyl, isopropyl, and tert-butyl crotonate took place with high stereocontrol about the new chiral centers providing the syn-1,2-amino alcohol products, syn-trans-γ-lactones 2 and 4, in excellent yields. Apparently, the stereochemical course of these reductive couplings is stereocontrolled by chelation of the Sm(III) cations

  该SMI 2 α-诱导的酮-烯烃偶联反应（烷氧基羰基）氨基酮1和3用甲基，乙基，异丙基和叔丁基巴豆酸发生有关提供新的手性中心的高立体控制合成-1,2- -氨基醇产品，顺-反-γ-内酯2和4，收率极高。显然，这些还原偶联的立体化学过程是通过与氨基甲酸酯基团附着在所得酮基自由基上的Sm（III）阳离子螯合来立体控制的。随着巴豆酸的酯的烷基的大小增加，立体选择性增加。特别地，当SmI 2时几乎仅获得2和4。-巴豆酸叔丁酯进行的1和3的偶合偶联。有趣的是，羟基基团的定向耦合诱导SMI 2用甲基，乙基，和异丙基用巴豆酸的非对映选择性完全逆转进行，几乎只提供的α羟基酮11的顺式-1,2-二醇产物，SYN -顺式-γ-内酯12。