1,1-anhydro-1-C-<2-(hydroxymethyl)-4,6-dimethoxyphenyl>-β-D-glucopyranose | 76843-39-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异香豆素
• 英文名称: 1,1-anhydro-1-C-<2-(hydroxymethyl)-4,6-dimethoxyphenyl>-β-D-glucopyranose
• 英文别名: (3S,3'R,4'S,5'S,6'R)-6'-(hydroxymethyl)-4,6-dimethoxyspiro[1H-2-benzofuran-3,2'-oxane]-3',4',5'-triol
• CAS: 76843-39-5
• 化学式: C₁₅H₂₀O₈
• 分子量: 328.319
• InChiKey: VYPOMEDOXQZIEJ-LFHLZQBKSA-N

物化性质

• 熔点：
  174 °C
• 沸点：
  606.7±55.0 °C(Predicted)
• 密度：
  1.51±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  118
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 1,1-anhydro-1-C-<2-(hydroxymethyl)-4,6-dimethoxyphenyl>-β-D-glucopyranose 在 吡啶 作用下， 反应 3.0h， 生成 1,1²-anhydro-1-C-<2-(hydroxymethyl)-4,6-dimethoxyphenyl>-β-D-glucopyranose tetraacetate
  参考文献：
  名称：

  Total Synthesis and Structural Elucidation of the Antifungal Agent Papulacandin D

  摘要：

  Condensation of the aryllithium reagents, prepared from the bromides 10 and 11 and tert-butyllithium, with lactone 19 and acid-catalyzed spirocyclization gave the papulacandin spiroketals 14 and 15. Subsequent protection using di-tert-butylsilyl bis(trifluoromethanesulfonate) gave the diols 31 and 30. Isoleucine (37) was converted using a double Wittig reaction sequence and propargylation of the intermediate aldehyde 46 into the alkynol 47. Separation of the C-7 epimers of 47 was achieved using kinetic resolution via Sharpless epoxidation. Both alkynol epimers 53 and 57 were converted into the papulacandin side chain esters 65 and 66 using a hydrozirconation and palladium(0)-catalyzed coupling sequence. Comparisons of Mosher ester derivatives of 65 and 66 with the Mosher ester derivative of the natural papulacandin side chain and further degradation were consistent with the stereochemistry of the natural product being 7S,14S. Esterification of the spiroketals with the mixed anhydride 70 and global deprotection gave papulacandin D (1).

  DOI：

  10.1021/jo951895e
• 作为产物：
  描述：

  (2-溴-3,5-二甲氧基苯基)甲醇 在 咪唑 、 Amberlite IR-120 、 叔丁基锂 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 46.5h， 生成 1,1-anhydro-1-C-<2-(hydroxymethyl)-4,6-dimethoxyphenyl>-β-D-glucopyranose
  参考文献：
  名称：

  Total Synthesis and Structural Elucidation of the Antifungal Agent Papulacandin D

  摘要：

  Condensation of the aryllithium reagents, prepared from the bromides 10 and 11 and tert-butyllithium, with lactone 19 and acid-catalyzed spirocyclization gave the papulacandin spiroketals 14 and 15. Subsequent protection using di-tert-butylsilyl bis(trifluoromethanesulfonate) gave the diols 31 and 30. Isoleucine (37) was converted using a double Wittig reaction sequence and propargylation of the intermediate aldehyde 46 into the alkynol 47. Separation of the C-7 epimers of 47 was achieved using kinetic resolution via Sharpless epoxidation. Both alkynol epimers 53 and 57 were converted into the papulacandin side chain esters 65 and 66 using a hydrozirconation and palladium(0)-catalyzed coupling sequence. Comparisons of Mosher ester derivatives of 65 and 66 with the Mosher ester derivative of the natural papulacandin side chain and further degradation were consistent with the stereochemistry of the natural product being 7S,14S. Esterification of the spiroketals with the mixed anhydride 70 and global deprotection gave papulacandin D (1).

  DOI：

  10.1021/jo951895e

文献信息

• Enantioselective Synthesis of the Papulacandin Ring System:  Conversion of the Mannose Diastereoisomer into a Glucose Stereoisomer
  作者：Devan Balachari、George A. O'Doherty

  DOI：10.1021/ol006662a

  日期：2000.12.1

  [structure] An enantioselective synthesis of three diastereoisomers of the C-arylglycoside tricyclic spiroketal nucleus of the papulacandins has been achieved, in which the initial asymmetry was introduced via a Sharpless dihydroxylation of substituted 5-aryl-2-vinylfurans. A selective oxidation-reduction sequence converted the mannose isomer into the glucose isomer. This sequence can conveniently

  [结构]已经实现了对木瓜素的C-芳基糖苷三环螺环核的三个非对映异构体的对映选择性合成，其中最初的不对称性是通过取代的5-芳基-2-乙烯基呋喃的Sharpless二羟基化引入的。选择性氧化还原序列将甘露糖异构体转化为葡萄糖异构体。该序列可以方便地从3，5-二甲氧基苄基醇以仅10-14步产生papulacandin环系统以及其对映异构体和非对映异构体，总产率为5-8％。
• C-Glycosides. 9. Stereospecific synthesis of C-glycosidic spiroketal of the papulacandins
  作者：Stanislas Czernecki、Marie Claude Perlat

  DOI：10.1021/jo00022a014

  日期：1991.10

  The reaction of ortho-lithiated triphenylmethyl benzyl ether with perbenzylated D-gluconolactone 1 followed by cyclization by BF3.Et2O provides a new stereospecific synthesis of C-glycosidic spiroketals. The structure of the peracetylated derivative was determined by X-ray diffraction. This methodology is applied to the synthesis of the spiroketal unit of papulacandins.
• Total Synthesis and Structural Elucidation of the Antifungal Agent Papulacandin D
  作者：Anthony G. M. Barrett、Michael Peña、J. Adam Willardsen

  DOI：10.1021/jo951895e

  日期：1996.1.1

  Condensation of the aryllithium reagents, prepared from the bromides 10 and 11 and tert-butyllithium, with lactone 19 and acid-catalyzed spirocyclization gave the papulacandin spiroketals 14 and 15. Subsequent protection using di-tert-butylsilyl bis(trifluoromethanesulfonate) gave the diols 31 and 30. Isoleucine (37) was converted using a double Wittig reaction sequence and propargylation of the intermediate aldehyde 46 into the alkynol 47. Separation of the C-7 epimers of 47 was achieved using kinetic resolution via Sharpless epoxidation. Both alkynol epimers 53 and 57 were converted into the papulacandin side chain esters 65 and 66 using a hydrozirconation and palladium(0)-catalyzed coupling sequence. Comparisons of Mosher ester derivatives of 65 and 66 with the Mosher ester derivative of the natural papulacandin side chain and further degradation were consistent with the stereochemistry of the natural product being 7S,14S. Esterification of the spiroketals with the mixed anhydride 70 and global deprotection gave papulacandin D (1).