methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranosonate | 195523-23-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranosonate
• 英文别名: methyl (3R)-3-hydroxy-3-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]propanoate
• CAS: 195523-23-0
• 化学式: C₁₅H₂₄O₈
• 分子量: 332.351
• InChiKey: FNLNFWIUSXUGNL-HFWJBDJDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranosonate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以79%的产率得到2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranose
  参考文献：
  名称：

  Synthesis of 2-deoxy-4-octulose derivatives by highly diastereoselective alkylations of protected hexuloses

  摘要：

  Reformatsky reaction of 2,3:4,5-di-O-isopropylidene-beta-D-arabino-hexos-2- ulopyranose 1 with methyl bromoacetate proceeded with high diastereoselectivity to give methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno-oct-4-ulo-4,8-pyranosonate 2 and its -D-gluco isomer 3, in an similar or equal to 10:1 ratio. Configurations of the new stereogenic centres (C-3) in 2 and 3 were determined by reduction of their ester groups to the related 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno- 4 and -D-gluco-oct-4-ulo-4,8-pyranose 5, respectively. When alkylation at C-1 of 1 was carried out with 2-lithio tert-butyl acetate, the corresponding tert-butyl ester of 2 (6) and 3 (7) were formed in an similar or equal to 5.4:1 ratio. The stereochemistry of 6 and 7 was established by their respective reductions to 4 and 5. On the other hand, reaction of 1 with methyl methoxycarbonylmethylenedimethylsulfurane gave only methyl 2,3-anhydro-4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto-oct-4-ulo-4,8-pyranosonate 8, whose stereochemistry was demonstrated by its transformation to 4. On the other hand, Reformatsky reaction of 2,3:4,6-di-O-isopropylidene-alpha-L-xylo-hexos-2-ulofuranose 10 with methyl bromoacetate proceeded with moderate diastereoselectivity to give methyl 2-deoxy-4,5:6,8-di-O-isopropylidene-alpha-L-gulo-oct-4-ulo-4,7-furanosonate 11 and its -L-ido isomer 12, in an similar or equal to 3.5:1 ratio. Configuration of the new stereogenic centre (C-3) in 11, and hence in 12, was determined by degradation to the known dimethyl D-methoxymalate (+)-13. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00266-8
• 作为产物：
  描述：

  果糖二丙酮 在 N-甲基吲哚酮 、 四丙基高钌酸铵 、 sodium hypobromide 、 4 Angstroem MS 、 L-脯氨酸 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 38.5h， 生成 methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-β-D-manno-oct-4-ulo-4,8-pyranosonate
  参考文献：
  名称：

  Highly stereocontrolled alkylation of protected ‘diacetone hexulose aldehydes’

  摘要：

  Claisen Schmidt aldol condensation (with acetone, catalysed by L- and D-proline), Knoevenagel reaction with acetoacetic acid and the modified Reformatsky reaction with bromoacetone of the 'diacetone hexulose aldehydes' 2 and 7 gave the corresponding beta -hydroxyketones 3 4 and 8-9 as well as the (E)-alpha,beta -enones 5 and 10, respectively. The highest chemo- and stereoselectivities were obtained with the Knoevenagel procedure using L-proline as the catalyst. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00488-8

文献信息

• Stereochemistry of addition of carbanion reagents to `diacetone fructose aldehyde'. Configurational assignment of a 1-deoxyheptulose derivative by X-ray crystallography and NMR studies directed to the assignment of isomeric adducts
  作者：Michael J Costanzo、Libuse Jaroskova、Diane A Gauthier、Bruce E Maryanoff

  DOI：10.1016/s0957-4166(99)00035-x

  日期：1999.2

  The addition of carbanionic reagents to `diacetone fructose aldehyde' (6) was investigated with a focus on the stereocontrol. The Grignard reagents, MeMgBr, EtMgBr, i-PrMgBr, and MeMgI, gave a high bias (≥90%) for one diastereomer, assigned as the R-isomer, in ether at −78 to 0°C. The reaction of PhMgBr showed diminished diastereoselectivity under these conditions, with a significant dependence of

  研究了向“双丙酮果糖醛”（6）中添加碳负离子试剂，重点是立体控制。格氏试剂MeMgBr，EtMgBr，i- PrMgBr和MeMgI在-78至0°C的乙醚中对一种被指定为R-异构体的非对映异构体具有很高的偏倚（≥90％）。在这些条件下，PhMgBr的反应显示出非对映选择性降低，且异构体比例对温度和溶剂的依赖性很大。PhCH 2 MgBr仅提供了“烯丙基重排”加合物，即13，其非对映异构控制差（约60:40）。MeLi，t -BuLi，PhLi和LiCH 2 CO 2 - t-Bu提供的6-加合物富集了80-89％的R-异构体，而2-lithio-2-ethyl-1,3-dithiane的R：S加合物比例为94：6 （15a：15b）。通过氨基磺酸衍生物2a的X射线分析建立了4a甲醇C1中心的R绝对立体化学。确定了Carbon-13 NMR化学位移标准（C1和C3的化学位移），以促进6的C1加合物的立体化学分配。
• 4-Octulose Derivatives; Part 8:¹Highly Stereocontrolled Synthesis of 2-Deoxy-4-octulosononitriles by Reformatsky-Type Reaction
  作者：Isidoro Izquierdo、María T. Plaza、Juan. A. Tamayo、Antonio J. Mota

  DOI：10.1055/s-2004-822328

  日期：——

  2-Deoxy-4,5:6,7-di-O-isopropylidene-β-d-manno-oct-4-ulo-4,8-pyranosononitrile (3) and 2-deoxy-4,5:6,8-di-O-isopropylidene-α-l-gulo-oct-4-ulo-4,7-furanosononitrile (5) were prepared by a high stereocontrolled indium-mediated Reformatsky-type reaction of 2,3:4,5-di-O-isopropylidene-β-d-arabino-hexos-2-ulopyranose (1) and 2,3:4,6-di-O-isopropylidene-α-l-xylo-hexos-2-ulofuranose (2) with bromoacetonitrile, repectively. The configurations at C(3) in 3 and 5 were established by chemical correlation.

  2-Deoxy-4,5:6,7-di-O-isopropylidene-β-d-manno-ct-4-ulo-4,8-pyranosonitrile (3) 和 2-Deoxy-4,5:6,8-di-O-isopropylidene-α-l-gulo-ct-4-ulo-4,7-furanosonitrile (5) 是由 2,3.4,5-di-O-isopropylidene-β-d-arabino-hexos-2-ulopyranose (1) 和 2,3:4,6-di-O-isopropylidene-β-d-manno-ct-4-ulo-4,8-pyranosonitrile (2) 通过高度立体可控的铟介导的 Reformatsky 型反应制备的：2,3:4,6-di-O-isopropidylene-α-l-xylo-hexos-2-ulofuranose (2) 与溴乙腈的 Reformatsky 型反应制备了 2,3:4,5-di-O-异亚丙基-δ-d-阿拉伯-己糖-2-吡喃糖 (1)和 2,3:4,6-di-O-异亚丙基-δ-l-氧基-己糖-2-呋喃糖 (2)。通过化学相关性确定了 3 和 5 中 C(3) 的构型。
• Highly stereocontrolled alkylation of protected ‘diacetone hexulose aldehydes’
  作者：Isidoro Izquierdo、Marı́a T. Plaza、Rafael Robles、Antonio J. Mota、Francisco Franco

  DOI：10.1016/s0957-4166(01)00488-8

  日期：2001.10

  Claisen Schmidt aldol condensation (with acetone, catalysed by L- and D-proline), Knoevenagel reaction with acetoacetic acid and the modified Reformatsky reaction with bromoacetone of the 'diacetone hexulose aldehydes' 2 and 7 gave the corresponding beta -hydroxyketones 3 4 and 8-9 as well as the (E)-alpha,beta -enones 5 and 10, respectively. The highest chemo- and stereoselectivities were obtained with the Knoevenagel procedure using L-proline as the catalyst. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Synthesis of 2-deoxy-4-octulose derivatives by highly diastereoselective alkylations of protected hexuloses
  作者：Isidoro Izquierdo、María T. Plaza、Rafael Robles、Antonio Mota

  DOI：10.1016/s0957-4166(97)00266-8

  日期：1997.8

  Reformatsky reaction of 2,3:4,5-di-O-isopropylidene-beta-D-arabino-hexos-2- ulopyranose 1 with methyl bromoacetate proceeded with high diastereoselectivity to give methyl 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno-oct-4-ulo-4,8-pyranosonate 2 and its -D-gluco isomer 3, in an similar or equal to 10:1 ratio. Configurations of the new stereogenic centres (C-3) in 2 and 3 were determined by reduction of their ester groups to the related 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno- 4 and -D-gluco-oct-4-ulo-4,8-pyranose 5, respectively. When alkylation at C-1 of 1 was carried out with 2-lithio tert-butyl acetate, the corresponding tert-butyl ester of 2 (6) and 3 (7) were formed in an similar or equal to 5.4:1 ratio. The stereochemistry of 6 and 7 was established by their respective reductions to 4 and 5. On the other hand, reaction of 1 with methyl methoxycarbonylmethylenedimethylsulfurane gave only methyl 2,3-anhydro-4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto-oct-4-ulo-4,8-pyranosonate 8, whose stereochemistry was demonstrated by its transformation to 4. On the other hand, Reformatsky reaction of 2,3:4,6-di-O-isopropylidene-alpha-L-xylo-hexos-2-ulofuranose 10 with methyl bromoacetate proceeded with moderate diastereoselectivity to give methyl 2-deoxy-4,5:6,8-di-O-isopropylidene-alpha-L-gulo-oct-4-ulo-4,7-furanosonate 11 and its -L-ido isomer 12, in an similar or equal to 3.5:1 ratio. Configuration of the new stereogenic centre (C-3) in 11, and hence in 12, was determined by degradation to the known dimethyl D-methoxymalate (+)-13. (C) 1997 Elsevier Science Ltd.