(2R,3R,3aS,7aS)-tetrahydro-3-hydroxy-2-phenyl-2H-furo[3,2-b]pyran-5(6H)-one | 158673-96-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃吡喃类
• 英文名称: (2R,3R,3aS,7aS)-tetrahydro-3-hydroxy-2-phenyl-2H-furo[3,2-b]pyran-5(6H)-one
• 英文别名: (+)-goniotharvesin；Goniotharvensin；(2R,3R,3aS,7aS)-3-hydroxy-2-phenyl-2,3,3a,6,7,7a-hexahydrofuro[3,2-b]pyran-5-one
• CAS: 158673-96-2
• 化学式: C₁₃H₁₄O₄
• 分子量: 234.252
• InChiKey: LKCVKUFQGOCQGT-WKSBVSIWSA-N

物化性质

• 沸点：
  476.9±45.0 °C(Predicted)
• 密度：
  1.298±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3R,3aS,7aS)-tetrahydro-3-hydroxy-2-phenyl-2H-furo[3,2-b]pyran-5(6H)-one 在 吡啶 、 2,6-二甲基吡啶 、 苯基溴化硒 、 四丁基氟化铵 、 双氧水 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.34h， 生成 全内酯
  参考文献：
  名称：

  An enantioselective total synthesis of (+)-altholactone from diethyl L-tartrate

  摘要：

  An enantioselective total synthesis of the cis-fused tetrahydrofurano-2-pyrone (+)-altholactone (1) from diethyl L-tartrate via the L-threitol derivative 2 is described. The remaining two stereogenic centers of 1 are introduced by a highly stereoselective hydroboration-oxidation sequence.

  DOI：

  10.1016/s0040-4020(01)89432-1
• 作为产物：
  描述：

  Toluene-4-sulfonic acid (S)-2-((S)-2,2-diethyl-[1,3]dioxolan-4-yl)-2-(4-methoxy-benzyloxy)-ethyl ester 在 吡啶 、 sodium hydroxide 、 copper(l) iodide 、 硼烷四氢呋喃络合物 、 二甲基硫 、 硫酸 、 双氧水 、 potassium carbonate 、 臭氧 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 60.5h， 生成 (2R,3R,3aS,7aS)-tetrahydro-3-hydroxy-2-phenyl-2H-furo[3,2-b]pyran-5(6H)-one
  参考文献：
  名称：

  An enantioselective total synthesis of (+)-altholactone from diethyl L-tartrate

  摘要：

  An enantioselective total synthesis of the cis-fused tetrahydrofurano-2-pyrone (+)-altholactone (1) from diethyl L-tartrate via the L-threitol derivative 2 is described. The remaining two stereogenic centers of 1 are introduced by a highly stereoselective hydroboration-oxidation sequence.

  DOI：

  10.1016/s0040-4020(01)89432-1

文献信息

• Stereoselective Ring Expansion of Vinyl Oxiranes: Mechanistic Insights and Natural Product Total Synthesis
  作者：Matthew Brichacek、Lindsay A. Batory、Jon T. Njardarson

  DOI：10.1002/anie.200906830

  日期：2010.2.22

  applicable, catalytic, and stereoselective vinyl oxirane ring expansion is described (see scheme; hfacac=hexafluoroacetylacetonate). The stereoselectivity was influenced by several reaction parameters, and kinetic studies support a mechanistic proposal involving the in situ formation of a more reactive catalytic species. This ring‐expansion reaction has been employed in the asymmetric total synthesis

  真是（紧张）的解脱！描述了第一个广泛适用的，催化的和立体选择性的乙烯基环氧乙烷环扩环（参见方案； hfacac =六氟乙酰丙酮酸酯）。立体选择性受几个反应参数的影响，动力学研究支持了一种机制性的提议，涉及原位形成更具反应性的催化物质。该扩环反应已用于（+）-邻苯二酚二醇的不对称全合成中。
• The Effect of Sulfoxides on the Stereoselective Construction of Tetrahydrofurans: Total Synthesis of (+)-Goniothalesdiol
  作者：Gloria Hernández-Torres、M. Carmen Carreño、Antonio Urbano、Françoise Colobert

  DOI：10.1002/chem.201002637

  日期：2011.1.24

  Good to excellent stereoselectivities were achieved in the reductive cyclization (with Et3SiH/trimethylsilyl trifluoromethanesulfonate (TMSOTf)) of enantiopure hydroxy sulfinyl ketones en route to 2,5‐cis‐disubstituted tetrahydrofuran skeletons. Electrostatic effects of the exocyclic sulfoxide, which stabilized the reactive intermediate oxocarbenium conformations, were responsible for the observed

  对映体纯的羟基亚磺酰基酮在2,5-顺式-二取代的四氢呋喃骨架的还原环化反应中（用Et 3 SiH /三甲基甲硅烷基三氟甲磺酸盐（TMSOTf））达到了良好的立体选择性。环外亚砜的静电作用使反应性中间体氧碳鎓构象稳定，这是观察到的立体控制的原因。提出了一个模型来解释结果。使用该反应和不对称还原β-酮亚砜作为关键步骤，促进了天然β-C-芳基糖苷（+）-goniothalesdiol的全部对映选择性合成。
• Styryl-lactone derivatives and alkaloids from Goniothalamus borneensis (Annonaceae)
  作者：Shu-Geng Cao、Xiao-Hua Wu、Keng-Yeow Sim、B.K.H. Tan、J.T. Pereira、Swee-Hock Goh

  DOI：10.1016/s0040-4020(97)10422-7

  日期：1998.3

  Twelve natural products, including two new compounds, goniothalesdiol 1a and goniothalactam 2, were isolated from the bark of the Malaysian tree Goniothalamus borneensis (Annonaceae) and evaluated for their cytotoxic activity. Their structures were elucidated by spectroscopy including 2D-NMR spectroscopy. 1a, which was semisynthesised from (+)-goniothalenol (3a), was related to several cytotoxic styryl-lactones

  十二天然产品，包括两个新的化合物，goniothalesdiol 1A和goniothalactam 2，从马来西亚树的树皮中分离哥纳香属囊螺（番荔枝），并评价它们的细胞毒活性。通过包括2D-NMR光谱在内的光谱阐明了它们的结构。1a是由（+）-goniothalenol（3a）半合成的，与从该物种中分离出的几种具有细胞毒性的苯乙烯基内酯（4-8）有关。
• Synthesis of (+)-goniothalesdiol and (+)-7-epi-goniothalesdiol
  作者：Matej Babjak、Peter Kapitán、Tibor Gracza

  DOI：10.1016/j.tet.2005.01.004

  日期：2005.2

  A total synthesis of (+)-goniothalesdiol, a 3,4-dihydroxy-2,5 -disubstituted tetrahydrofuran isolated from Goniothalamus borneensis (Annonaceae), and its 7-epimer is reported using oxycarbonylation methodology for construction of polyhydroxylated substituted heterocycles. Diastereoselectivity of addition of organometallic reagents to 2,3-O-isopropylidene-D-threose derivatives using theoretical calculations based on the semiempirical PM5 was studied. (C) 2005 Elsevier Ltd. All rights reserved.
• Stereoselective Total Synthesis of Bioactive Styryllactones (+)-Goniofufurone, (+)7-<i>epi</i>-Goniofufurone, (+)-Goniopypyrone, (+)-Goniotriol, (+)-Altholactone, and (−)-Etharvensin
  作者：Kavirayani R. Prasad、Shivajirao L. Gholap

  DOI：10.1021/jo0702342

  日期：2008.1.1

  [GRAPHICS]Stereoselective total synthesis of biologically active styryllactones 7-epi-goniofufurone, goniofufurone, goniopypyrone, goniotriol, altholactone, and etharvensin was achieved in high overall yields from a common intermediate derived from D-(-)-tartaric acid. It is based on the utility of a masked tetrol, comprising an alkene tether and four contiguous hydroxy groups. The pivotal reaction sequence involves hydroxy-directed lactonization via the oxidation of alkene, and subsequent elaboration to styryllactones. The masked tetrol was prepared by the extension of gamma-phenyl-gamma-hydroxy butyramide, readily obtained from the bis-dimethylamide of tartaric acid, employing a combination of selective Grignard additions and a stereoselective reduction.