2,3,5,6,7-penta-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone | 10279-92-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,3,5,6,7-penta-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone
• 英文别名: [(2R,3R)-2,3-dibenzoyloxy-3-[(2S,3R,4R)-3,4-dibenzoyloxy-5-oxooxolan-2-yl]propyl] benzoate
• CAS: 10279-92-2
• 化学式: C₄₂H₃₂O₁₂
• 分子量: 728.709
• InChiKey: PNZZGLGHZSOXSE-SQGINLDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  54
• 可旋转键数：
  18
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  158
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  2,3,5,6,7-penta-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone 在 palladium on activated charcoal 三氟化硼乙醚 、 氢气 、 二(3-甲基丁烷-2-基)硼烷 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 25.0 ℃ 、304.0 kPa 条件下， 反应 26.0h， 生成 methyl 2,5,6,7-tetra-O-benzoyl-3-deoxy-β-D-gluco-heptofuranoside
  参考文献：
  名称：

  Synthesis of crystalline derivatives of 3-deoxy-d-gluco-heptofuranose

  摘要：

  DOI：

  10.1016/0008-6215(87)80277-x
• 作为产物：
  描述：

  葡庚糖酸内酯 、 alkaline earth salt of/the/ methylsulfuric acid 生成 2,3,5,6,7-penta-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone
  参考文献：
  名称：

  Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from d-Glucoheptono-1,4-lactone

  摘要：

  Enantiomerically pure (2R,4S)-4-hydroxypipecolic acid [(+)-1] was synthesized from D-glucoheptono-1,4-lactone (2) via the 3,5-dideoxy-D-xylo-heptono-1,4-lactone (7). The latter was readily prepared by benzoylation of 2, followed by p-elimination and diastereoselective hydrogenation of the resulting furanones (4). Compound 7 was converted into the 6,7-O-eyclohexylidene derivative 11, which on treatment with tosyl chloride for long periods afforded the 2-chloro derivative 14, the precursor of the azide 15. Hydrogenolysis of 15 and protection of the amine gave the N-benzyloxycarbonyl derivative 19, having the required configuration for the stereocenters at C-2 and C-4. Removal of the cyclohexylidene group by hydrolysis and subsequent oxidative degradation of the resulting glycol system afforded the hexurono-6,3-lactone 21 as a key intermediate. Chemoselective reduction of the aldehyde function of 21 led to the alcohol 23, which was derivatized as the mesylate 24. Releasing of the amino group by hydrogenation, and dissolution of resulting 25 in aqueous alkali, promoted the intramolecular nucleophilic displacement of the mesylate to give (+)-1. Its enantiomer [(-)-1] was prepared by a similar sequence starting from 2.

  DOI：

  10.1021/jo990445+

文献信息

• A Carbohydrate Approach to the Enantioselective Synthesis of 1,3-Polyols
  作者：Christián Di Nardo、Lucio O. Jeroncic、Rosa M. de Lederkremer、Oscar Varela

  DOI：10.1021/jo960042z

  日期：1996.1.1

  obtained from 2 ( approximately 90% yield) as a mixture of the E and Z diastereoisomers, which were separated by column chromatography or, more efficiently, by HPLC. The catalytic hydrogenation of compounds 4-E and 4-Z took place diastereoselectively, due to the chiral induction of the stereocenter located in the lateral chain. Thus, hydrogenation of 4-E led to a mixture of the 4,5-dihydro-(3H)-furan-2-ones

  用叔胺处理过-O-苯甲酰基-D-甘油-D-gulo-庚酮-1,4-内酯（2）（5H）-呋喃-2-一衍生物3，4，和5，分别通过控制消除1、2或3个苯甲酸分子而形成。通过NMR技术确定4和5的环外双键的立体化学。特别地，呋喃酮4是从2（约90％收率）作为E和Z非对映异构体的混合物获得的，其通过柱色谱法或更有效地通过HPLC分离。由于位于侧链的立体中心的手性诱导，化合物4-E和4-Z的催化氢化是非对映选择性的。因此，4-E的氢化导致具有3R，5S，2'S（D-木糖基）的4,5-二氢-（3H）-呋喃-2-酮的混合物 6）和3S，5R，2'S（D-arabino，7）配置，其中6为主要产品；而4-Z异构体给出的混合物相同，但优势为7。最初的4-E / Z混合物加氢后，重结晶后即可获得纯净的化合物6。6gave 9的O-脱苯甲酰化作用，用NaBH（4）还原为3,5-二脱氧-间-二甲苯基-庚醇（11）
• Bromination of sugar enones and enonolactones
  作者：Christían Di Nardo、Oscar Varela、Rosa M. de Lederkremer、Ricardo F. Baggio、Daniel R. Vega、María T. Garland

  DOI：10.1016/0008-6215(94)00352-g

  日期：1995.4

  Bromination of 2,4,6-tri-O-benzoyl-3-deoxy-D-erytro-hex-2-enono-1,5-lactone (1) took place diastereoselectively to afford a single product: 2,4,6-tri-O-benzoyl-2,3-dibromo-3-deoxy-D-altrofio-1,5-lactone (2). The configuration of C-2 and C-3 was determined as R,R by NMR spectroscopy and taking into account considerations of the stereochemical course of the bromination. The configuration of 2 was confirmed by X-ray analysis, which also revealed that the conformation of the lactone ring consists of a H-4(3)(D) distorted half-chair. The bromine addition to 2,5,6,7-tetra-O-benzoyl-D-arabino-hept-2-enone-1,4-lactone (5), readily prepared by DBU-promoted elimination from the perbenzoylated lactone derivative 4, was also diastereoselective and led to the dibromo derivative 6, whose configuration for C-2 and C-3 was assigned as S,S. Bromination of the alpha,beta-unsaturated carbonyl system of 2-propyl 6-O-acetyl-3,4-dideoxy-alpha-oglycero-hex-3-enopyranosid-2-ulose (7) afforded an unsaturated monobromo derivative: 2-propyl 6-O-acetyl-3-bromo-3,4-dideoxy-alpha-D-glycero-hex-3-enopyranosid-2-ulose (8), suggesting that dehydrobromination occurred after addition of bromine.
• β-Elimination in aldonolactones. Structure of the furan-2-one derivative obtained by benzoylation of ----heptono-1,4-lactone
  作者：Lucio O. Jeroncic、Oscar J. Varela、Alicia Fernandez Cirelli、Rosa M. De Lederkremer

  DOI：10.1016/s0040-4020(01)82428-5

  日期：1984.1