methyl 4,6-O-benzylidene-2,3-dideoxy-3-C-methyl-3,2-C-(2'-oxapropan-1'-yl-3'-ylidene)-α-D-arabino-hexopyranoside | 171076-03-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: methyl 4,6-O-benzylidene-2,3-dideoxy-3-C-methyl-3,2-C-(2'-oxapropan-1'-yl-3'-ylidene)-α-D-arabino-hexopyranoside
• 英文别名: (1S,2R,7S,9R,12R)-7-methoxy-2-methyl-12-phenyl-8,11,13-trioxatricyclo[7.4.0.02,6]tridec-5-en-4-one
• CAS: 171076-03-2
• 化学式: C₁₈H₂₀O₅
• 分子量: 316.354
• InChiKey: WJTCLCHRCVVGOU-HSFUPAIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-2,3-dideoxy-3-C-methyl-3,2-C-(2'-oxapropan-1'-yl-3'-ylidene)-α-D-arabino-hexopyranoside 在 N-溴代丁二酰亚胺(NBS) 、 barium carbonate 作用下， 以 四氯化碳 为溶剂， 反应 3.0h， 以72%的产率得到4-benzoyloxy-5-bromomethyl-2,3-C-(2-propen-2'-one)-3-deoxy-3-C-methyl-α-D-arabino-hexopyranosid-2-ulose
  参考文献：
  名称：

  The Stereoselective Preparation of an Enantiomerically Pure Cyclopentane Using Intramolecular Aldol Cyclopentaannulation of a Glucose Derivative

  摘要：

  Methods for the annulation of carbohydrates have found extensive applications in organic synthesis. We report here a new protocol for the stereoselective conversion of glucose into an enantiomerically pure cyclopentane aldehyde 22. The readily available epoxide 15 was reacted with allyl Grignard to produce alcohol 16 in 86% yield. Swern oxidation followed by epimerization using triethylamine in N,N-dimethylformamide furnished the ketone 17 also in 86% yield. Regioselective deprotonation with lithium hexamethyldisilazane in THF was followed by methylation with methyl iodide and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone as cosolvent to give 80% yield of ketone 18. Oxidation of ketone 18 by the Wacker procedure gave the 1,4-diketone 19 in 56% yield. Intramolecular aldol condensation occurred readily on treatment of diketone 19 with potassium tert-butoxide in toluene to furnish a 90% yield of enone 20. Treatment with N-bromosuccinimide produced the bromoester 21 in 72% yield, which was reduced to a mixture of aldehydes 22 (61%) and 23 (14%) with zinc shot in 2-propanol.

  DOI：

  10.1021/jo981225j
• 作为产物：
  描述：

  methyl 2,3-anhydro-4,6-O-benzilidene-α-D-mannopyranoside 在 N,N-二甲基丙烯基脲 、 potassium tert-butylate 、 氧气 、 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 、 copper dichloride 、 palladium dichloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 53.0h， 生成 methyl 4,6-O-benzylidene-2,3-dideoxy-3-C-methyl-3,2-C-(2'-oxapropan-1'-yl-3'-ylidene)-α-D-arabino-hexopyranoside
  参考文献：
  名称：

  The Stereoselective Preparation of an Enantiomerically Pure Cyclopentane Using Intramolecular Aldol Cyclopentaannulation of a Glucose Derivative

  摘要：

  Methods for the annulation of carbohydrates have found extensive applications in organic synthesis. We report here a new protocol for the stereoselective conversion of glucose into an enantiomerically pure cyclopentane aldehyde 22. The readily available epoxide 15 was reacted with allyl Grignard to produce alcohol 16 in 86% yield. Swern oxidation followed by epimerization using triethylamine in N,N-dimethylformamide furnished the ketone 17 also in 86% yield. Regioselective deprotonation with lithium hexamethyldisilazane in THF was followed by methylation with methyl iodide and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone as cosolvent to give 80% yield of ketone 18. Oxidation of ketone 18 by the Wacker procedure gave the 1,4-diketone 19 in 56% yield. Intramolecular aldol condensation occurred readily on treatment of diketone 19 with potassium tert-butoxide in toluene to furnish a 90% yield of enone 20. Treatment with N-bromosuccinimide produced the bromoester 21 in 72% yield, which was reduced to a mixture of aldehydes 22 (61%) and 23 (14%) with zinc shot in 2-propanol.

  DOI：

  10.1021/jo981225j

文献信息

• The synthesis and X-ray crystal structure of a cyclopentaannulated sugar; the first example of an intramolecular aldol cyclopentaannulation in carbohydrate chemistry
  作者：Andrew J. Wood、Paul R. Jenkins、John Fawcett、David R. Russell

  DOI：10.1039/c39950001567

  日期：——

  A 1,4-dicarbonyl compound 5 has been constructed by a sequence involving opening of a protected glucose epoxide with allyl magnesium chloride, alkylation and Wacker oxidation; the 1,4-dicarbonyl compound readily undergoes cyclisalion under basic conditions to produce a Cyclopentaannulated sugar derivative 6, whose structure was confirmed by X-ray crystallography.

  在碱性条件下，1,4-二羰基化合物很容易发生环化反应，生成环戊二烯糖衍生物 6。
• The first example of a highly stereoselective intramolecular radical cyclisation of a cyclopentenol derivative
  作者：Paul R. Jenkins、Andrew J. Wood

  DOI：10.1016/s0040-4039(97)00211-6

  日期：1997.3

  Silyl methylene radical cyclisation of a β-allylic cyclopentaannulated derivative of glucose leads to a single cis fused tricyclic ring system whereas the same cyclisation of the corresponding α derivative leads to a mixture of cis and trans fused products. These results can be explained by the preference for the formation of the cis fused 5,6-ring system even when this does not involve reaction from

  葡萄糖的β-烯丙基环戊环化衍生物的甲硅烷基亚甲基环化导致单个顺式稠合的三环系统，而相应α衍生物的相同环化导致顺式和反式稠合产物的混合物。这些结果可以通过优选形成顺式稠合的5，6-环系统来解释，即使这不涉及从分子的最小受阻侧进行反应。
• The Stereoselective Preparation of an Enantiomerically Pure Cyclopentane Using Intramolecular Aldol Cyclopentaannulation of a Glucose Derivative
  作者：Andrew J. Wood、David J. Holt、Maria-Consuelo Dominguez、Paul R. Jenkins

  DOI：10.1021/jo981225j

  日期：1998.11.1

  Methods for the annulation of carbohydrates have found extensive applications in organic synthesis. We report here a new protocol for the stereoselective conversion of glucose into an enantiomerically pure cyclopentane aldehyde 22. The readily available epoxide 15 was reacted with allyl Grignard to produce alcohol 16 in 86% yield. Swern oxidation followed by epimerization using triethylamine in N,N-dimethylformamide furnished the ketone 17 also in 86% yield. Regioselective deprotonation with lithium hexamethyldisilazane in THF was followed by methylation with methyl iodide and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone as cosolvent to give 80% yield of ketone 18. Oxidation of ketone 18 by the Wacker procedure gave the 1,4-diketone 19 in 56% yield. Intramolecular aldol condensation occurred readily on treatment of diketone 19 with potassium tert-butoxide in toluene to furnish a 90% yield of enone 20. Treatment with N-bromosuccinimide produced the bromoester 21 in 72% yield, which was reduced to a mixture of aldehydes 22 (61%) and 23 (14%) with zinc shot in 2-propanol.