(5R,6R,8R,9R,4'R)-6-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-8,9-dimethylmethylenedioxy-1,7-dioxa-3-azaspiro[4.4]nonan-2-one | 1161856-07-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5R,6R,8R,9R,4'R)-6-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-8,9-dimethylmethylenedioxy-1,7-dioxa-3-azaspiro[4.4]nonan-2-one
• 英文别名: (3R)-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5'-oxazolidin)-2'-one
• CAS: 1161856-07-0
• 化学式: C₁₄H₂₁NO₇
• 分子量: 315.323
• InChiKey: IXPDDAWYNGOBCT-AAYQSVHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.49
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  84.48
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1,4-二溴丁烷 、 (5R,6R,8R,9R,4'R)-6-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-8,9-dimethylmethylenedioxy-1,7-dioxa-3-azaspiro[4.4]nonan-2-one 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 1.42h， 以82%的产率得到(3R)-3'-bromobutyryl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5'-oxazolidin)-2'-one
  参考文献：
  名称：

  A practical access to glucose- and allose-based (5+5) 3-spiropseudonucleosides from a common intermediate

  摘要：

  A practical access to glucose-based and allose-based spirooxazolidinones is reported. The synthetic sequence consisting of TEMPO-catalyzed oxidation of 1,2: 5,6-di-O-isopropylidene-alpha-D-glucofuranose, Henry reaction, and reduction provides amino alcohol with allo-configuration on a multigram scale. Alternatively, water elimination from Henry products followed by a rehydration gives an access to diastereomerically pure glucose-based nitro alcohol which upon reduction provides complementary amino alcohol with gluco-configuration. The latter amino alcohols are transformed into spirooxazolidinones (3-spiropseudonucleosides) via their N-Cbz or N-phenylcarbamate derivatives. The title compounds easily undergo N-derivatization and give highly crystalline materials. Two of the newly obtained (5+5) 3-spiropseudonucleosides are characterized by X-ray crystallography. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2013.04.008
• 作为产物：
  描述：

  3-C-(N-phenyloxycarbonyl)aminomethyl-1,2:5,6-di-O-isopropylidene-α-D-allofuranose 在 苄基三乙基氯化铵 、 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.33h， 以80%的产率得到(5R,6R,8R,9R,4'R)-6-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-8,9-dimethylmethylenedioxy-1,7-dioxa-3-azaspiro[4.4]nonan-2-one
  参考文献：
  名称：

  A practical access to glucose- and allose-based (5+5) 3-spiropseudonucleosides from a common intermediate

  摘要：

  A practical access to glucose-based and allose-based spirooxazolidinones is reported. The synthetic sequence consisting of TEMPO-catalyzed oxidation of 1,2: 5,6-di-O-isopropylidene-alpha-D-glucofuranose, Henry reaction, and reduction provides amino alcohol with allo-configuration on a multigram scale. Alternatively, water elimination from Henry products followed by a rehydration gives an access to diastereomerically pure glucose-based nitro alcohol which upon reduction provides complementary amino alcohol with gluco-configuration. The latter amino alcohols are transformed into spirooxazolidinones (3-spiropseudonucleosides) via their N-Cbz or N-phenylcarbamate derivatives. The title compounds easily undergo N-derivatization and give highly crystalline materials. Two of the newly obtained (5+5) 3-spiropseudonucleosides are characterized by X-ray crystallography. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2013.04.008

文献信息

• Stereocontrolled synthesis of (5+5), (5+6) and (6+6) 3-spiropseudonucleosides
  作者：Consolación Gasch、José M. Illangua、Penélope Merino-Montiel、José Fuentes

  DOI：10.1016/j.tet.2009.03.038

  日期：2009.5

  3-Spiropseudonucleosides, in which the heterocyclic base is a five-membered (oxazolidine, imidazolidine, thiohydantoin) or six-membered (perhydrooxazine) heterocycle, have been prepared starting from a hexofuranos-3-ulose. The method leads to good yields and is completely stereoselective. The key intermediate is a sugar iso(thio)cyanate.

  已经从六呋喃糖-3-基糖开始制备了3-螺伪假核苷，其中杂环碱基是五元（恶唑烷，咪唑烷，硫代乙内酰脲）或六元（全氢恶嗪）杂环。该方法产生了良好的产率，并且是完全立体选择性的。关键中间体是糖异（硫）氰酸酯。