methyl (E)-[(3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethylperhydrodi[1,3]dioxolo[4,5-b:4,5-d]pyran-5-yl]-2-propenoate | 71553-87-2

• 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 (E)-[(3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethylperhydrodi[1,3]dioxolo[4,5-b:4,5-d]pyran-5-yl]-2-propenoate
• 英文别名: metrhyl (E)-6,7-dideoxyl-1,2:3,4-di-O-isopropylidene-α-D-galacto-oct-5-enopyranuronate；methyl (E)-3-[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]prop-2-enoate
• CAS: 71553-87-2
• 化学式: C₁₅H₂₂O₇
• 分子量: 314.335
• InChiKey: PMZYDSODWDSHNU-CBQMWPMMSA-N

物化性质

• 沸点：
  395.5±42.0 °C(predicted)
• 密度：
  1.195±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (E)-[(3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethylperhydrodi[1,3]dioxolo[4,5-b:4,5-d]pyran-5-yl]-2-propenoate 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 、 xylene 为溶剂， 反应 2.0h， 生成 N-Benzyl-2,2,2-trifluoro-N-[(R)-1-((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran-5-yl)-allyl]-acetamide
  参考文献：
  名称：

  Stereocontrolled introduction of an amino group at C-6 of d-galactose via (3,3)-sigmatropic rearrangements—novel synthesis of lincosamine and 7-epi-lincosamine precursors

  摘要：

  A new and stereoselective route to the aminoglycoside components of the antibiotics lincomycin and clindamycin is presented, The key step involves diastereoselective introduction of the amino group at C-6 of D-galactose by (3,3)-sigmatropic rearrangements of the corresponding allylic (Z)-trifluoroacetimidate and (Z)- and (E)-allylic thiocyanates. Epoxidation of the resulting trifluoroacetamide with m-CPBA led to the epoxide with high threo-selectivity. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)02110-3
• 作为产物：
  描述：

  D-吡喃葡萄糖 以 甲醇 为溶剂， 反应 8.0h， 生成 methyl (E)-[(3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethylperhydrodi[1,3]dioxolo[4,5-b:4,5-d]pyran-5-yl]-2-propenoate
  参考文献：
  名称：

  Valverde, Serafin; Herradon, Bernardo; Rabanal, Rosa M., Canadian Journal of Chemistry, 1987, vol. 65, p. 332 - 338

  摘要：

  DOI：

文献信息

• Use of Lithium Hexafluoroisopropoxide as a Mild Base for Horner−Wadsworth−Emmons Olefination of Epimerizable Aldehydes
  作者：Landy K. Blasdel、Andrew G. Myers

  DOI：10.1021/ol051785m

  日期：2005.9.1

  [reaction: see text] The weak base lithium 1,1,1,3,3,3-hexafluoroisopropoxide (LiHFI) is shown to be highly effective as a reagent for intermolecular Horner-Wadsworth-Emmons (HWE) olefination of epimerizable aldehydes with trimethyl phosphonoacetate, affording products with little or no epimerization and notably high E-selectivity.

  [反应：请参见文本]弱碱1,1,1,3,3,3-六氟异丙醇锂（LiHFI）被证明可高效地用作可扩散醛的分子间Horner-Wadsworth-Emmons（HWE）烯化反应的试剂。三甲基膦酰基乙酸酯，提供几乎没有或没有差向异构化的产物，并且具有很高的E选择性。
• Synthesis of<i>β</i>-Peptides with<i>β</i>-Helices from New C-Linked Carbo-<i>β</i>-Amino Acids: Study on the Impact of Carbohydrate Side Chains
  作者：Gangavaram V. M. Sharma、Kota Sudhakar Rao、Rapolu Ravi、Kongari Narsimulu、Pendem Nagendar、Chirutha Chandramouli、Singarapu Kiran Kumar、Ajit C. Kunwar

  DOI：10.1002/asia.200800249

  日期：2009.1.5

  The design and synthesis of β‐peptides from new C‐linked carbo‐β‐amino acids (β‐Caa) presented here, provides an opportunity to understand the impact of carbohydrate side chains on the formation and stability of helical structures. The β‐amino acids, Boc‐(S)‐β‐Caa(g)‐OMe 1 and Boc‐(R)‐β‐Caa(g)‐OMe 2, having a D‐galactopyranoside side chain were prepared from D‐galactose. Similarly, the homo C‐linked

  本文介绍的由新的C连接的碳-β-氨基酸（β- Caa）设计和合成β肽，为了解碳水化合物侧链对螺旋结构的形成和稳定性的影响提供了机会。该β -氨基酸，将Boc-（小号） - β -Caa （克） -OMe 1和制备Boc-（[R ）- β -Caa （克） -OMe 2中，具有d -galactopyranoside侧链从制备d -半乳糖。同样，均由C相连的碳β-氨基酸（β-hCaa）; Boc-（S）-β- hCaa （x） -OMe 3和Boc-（R）-β- hCaa （x） -OMe 4由D-葡萄糖制备。通过NMR，CD和MD研究研究了衍生自上述单体的肽。该β -肽，特别是从差向异构（在胺立体中心C中获得的短的β）1和2由手性交替的概念，显示出更小的倾向，以形成12分之10螺旋。螺旋线的这种实质性失稳可以归因于较大的D-吡喃半乳糖苷侧链。我们制备3和4交替的肽的努力没有成功。然而，β
• VALVERDE, SERAFIN MARTIN-LOMAS MANUEL;HERRADON, BERNARDO;GARCIA-OCHOA, SI+, TETRAHEDRON, 43,(1987) N 8, 1895-1901
  作者：VALVERDE, SERAFIN MARTIN-LOMAS MANUEL、HERRADON, BERNARDO、GARCIA-OCHOA, SI+

  DOI：——

  日期：——
• Stereocontrolled introduction of an amino group at C-6 of d-galactose via (3,3)-sigmatropic rearrangements—novel synthesis of lincosamine and 7-epi-lincosamine precursors
  作者：Jozef Gonda、Eva Zavacká、Miloslav Budešı́nský、Ivana Cı́sarová、Jaroslav Podlaha

  DOI：10.1016/s0040-4039(99)02110-3

  日期：2000.1

  A new and stereoselective route to the aminoglycoside components of the antibiotics lincomycin and clindamycin is presented, The key step involves diastereoselective introduction of the amino group at C-6 of D-galactose by (3,3)-sigmatropic rearrangements of the corresponding allylic (Z)-trifluoroacetimidate and (Z)- and (E)-allylic thiocyanates. Epoxidation of the resulting trifluoroacetamide with m-CPBA led to the epoxide with high threo-selectivity. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Valverde, Serafin; Herradon, Bernardo; Rabanal, Rosa M., Canadian Journal of Chemistry, 1987, vol. 65, p. 332 - 338
  作者：Valverde, Serafin、Herradon, Bernardo、Rabanal, Rosa M.、Martin-Lomas, Manuel

  DOI：——

  日期：——