(1aS,3R,3aS,6aS,6bR)-3-Triisopropylsilanyloxymethyl-tetrahydro-1,2,4,6-tetraoxa-cyclopropa[e]inden-5-one | 149625-81-0

• 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: (1aS,3R,3aS,6aS,6bR)-3-Triisopropylsilanyloxymethyl-tetrahydro-1,2,4,6-tetraoxa-cyclopropa[e]inden-5-one
• 英文别名: (1S,2R,4S,6R,7S)-6-[tri(propan-2-yl)silyloxymethyl]-3,5,8,10-tetraoxatricyclo[5.3.0.02,4]decan-9-one
• CAS: 149625-81-0
• 化学式: C₁₆H₂₈O₆Si
• 分子量: 344.48
• InChiKey: SJLUDRQKDOCJMC-GZBLMMOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.21
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  66.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1aS,3R,3aS,6aS,6bR)-3-Triisopropylsilanyloxymethyl-tetrahydro-1,2,4,6-tetraoxa-cyclopropa[e]inden-5-one 在 lithium hydroxide 、 四丁基氟化铵 、 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 生成 (25R)-5α-spirostan-3β-ol 3-O-β-D-galactopyranoside
  参考文献：
  名称：

  Application of the glycal assembly strategy to the synthesis of a branched oligosaccharide: the first synthesis of a complex saponin

  摘要：

  DOI：

  10.1021/ja00071a077
• 作为产物：
  描述：

  2,6-脱水-5-脱氧-3,4-O-(氧代亚甲基)-1-O-(三异丙基硅烷基)-D-阿拉伯糖-己-5-烯糖 在 二甲基二环氧乙烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 生成 (1aS,3R,3aS,6aS,6bR)-3-Triisopropylsilanyloxymethyl-tetrahydro-1,2,4,6-tetraoxa-cyclopropa[e]inden-5-one
  参考文献：
  名称：

  人类乳腺肿瘤 (Globo-H) 抗原的全合成和结构证明

  摘要：

  Hakomori MBr1 抗原的全合成，在人类乳腺肿瘤上大量表达，是相关的。该构建涉及四种糖基的组装：（17（两次）、18、20 和 26）和 l-岩藻糖衍生物，34。作为状态函数的末端半乳糖环磺酰氨基半乳糖基化立体化学的敏感性在关键步骤中利用其C4醇的保护状态。（参见化合物 51 的形成。）该合成用于确认 Hakomori 结构的分配，并为免疫偶联铺平了道路。（见化合物 64。）

  DOI：

  10.1021/ja962048b

文献信息

• Synthesis of Asialo GM₁. New Insights in the Application of Sulfonamidoglycosylation in Oligosaccharide Assembly:  Subtle Proximity Effects in the Stereochemical Governance of Glycosidation
  作者：Ohyun Kwon、Samuel J. Danishefsky

  DOI：10.1021/ja9724957

  日期：1998.2.1

  The total synthesis of asialo GM(1) (1a) has been accomplished, Using related chemistry, the methyl glycoside of the asialo compound (1b) has also been synthesized. These kinds of compounds have been identified as potential ligands for bacterial and viral infection sites, A simpler structure, which hits also been identified for its infection attracting structure in the context of glycopeptides and glycolipids (methyl glycoside 2), has also been synthesized. The key common phase in the syntheses involves the sulfonamidoglycosidation reaction which is used to create a beta-linkage leading to a galNAc residue joined to the C-4 hydroxyl group of a galactose unit either as a monosaccharide (see compound 2) or as C-4' in the contest of a lactosyl moiety, During the course of these studies there was encountered an unusual "proximal hydroxyl" directing effect. Thus, when C-4 on the galactose ring of an azaglycosylating donor bears a free hydroxyl (see, for instance, compound 13), beta-glycoside formation predominates. When this hydroxyl group is blocked, the process tends in the direction of alpha-glycoside formation (see compound 32), These findings were explained as arising from a critical intramolecular hydrogen bond between the C-4 axial hydroxyl of the galactose donor and its proximal pyranosidal ring oxygen. This interaction stabilizes conformations from which beta-glycosidation predominates.
• A total synthesis of a stage specific pentasaccharide embryogenesis marker
  作者：Tae Kyo Park、In Jong Kim、Samuel J. Danishefsky

  DOI：10.1016/0040-4039(95)01962-h

  日期：1995.12

  A thioglycoside coupling mediated by methyl triflate was used to generate Stage Specific Embryonic Antigen-3.
• First Synthesis of a Digitalis Saponin. Demonstration of the Scope and Limitations of a Convergent Scheme for Branched Oligosaccharide Synthesis by the Logic of Glycal Assembly
  作者：John T. Randolph、Samuel J. Danishefsky

  DOI：10.1021/ja00126a010

  日期：1995.5

  The synthesis of complex glycosides, with branching at C-2, is demonstrated. The key element involves the use of a 1,2-oxirane donor. Upon glycosylation, a C-2 hydroxyl is exposed to serve as the acceptor in the next glycosylation. Branching at C-2 with a beta-linked glycoside at C-1 was not achievable with epoxy 23 donor, but was accomplished with fluoro donor 25, in turn derived from 23. (See 19 + 18 --> 20; 20 + 25 --> 26. Compound 26 was deprotected to complete the first total synthesis of a natural saponin, desgalactotigonin (3)). A limitation in stereospecifity in the use of donor 23 and monoprotected galactal acceptor 28 was also encountered.
• Synthetic and Immunological Studies on Clustered Modes of Mucin-Related Tn and TF O-Linked Antigens:  The Preparation of a Glycopeptide-Based Vaccine for Clinical Trials against Prostate Cancer
  作者：Scott D. Kuduk、Jacob B. Schwarz、Xiao-Tao Chen、Peter W. Glunz、Dalibor Sames、Govindaswami Ragupathi、Philip O. Livingston、Samuel J. Danishefsky

  DOI：10.1021/ja9825128

  日期：1998.12.1

  The syntheses of two tumor-associated carbohydrate antigens, Tn and TF, have been achieved using glycal assembly and cassette methodologies. These synthetic antigens were subsequently clustered (c) and immunoconjugated to a carrier protein (KLH or BSA) or a synthetic lipopeptide (pam) for immunological study. Three Tn conjugates were used to vaccinate groups of mice, and all preparations proved to be immunogenic. The Tn(c) covalently linked to KLH (27-KLH) plus the adjuvant QS-21 was the optimal vaccine, inducing high median IgM and IgG titers against Tn(c) by ELISA. These antibodies were strongly reactive with the Tn(c) positive human colon cancer cell line LS-C but not the Tn(c) negative colon cancer cell Line LS-B by FAGS. The antibodies' reactivities with natural antigens were inhibited with synthetic Tn(c) but not with structurally unrelated compounds. On the basis of these results, vaccines containing 27-KLH and 30-pam plus QS-21 are being tested in patients with prostate cancer.
• A highly convergent synthesis of an N-linked glycopeptide presenting the H-type 2 human blood group determinant
  作者：Zhi-Guang Wang、J. David Warren、Vadim Y. Dudkin、Xufang Zhang、Ulrich Iserloh、Michael Visser、Matthias Eckhardt、Peter H. Seeberger、Samuel J. Danishefsky

  DOI：10.1016/j.tet.2006.02.080

  日期：2006.5

  The total synthesis of an H-type blood group determinant in a model biological setting is described. The construct is comprised of a high mannose core structure with projecting lactose spacers, culminating in a two-copy presentation of the H-type blood group determinant itself. Key reactions that were used in this construction include sulfonamidohydroxylation (see 15 -> 18) and benzoate-directed glycosylation via an activated thiophenyl donor (see 34 -> 36). Another key strategic element involved the epimerization of an interior core glucoside to reach the P-mannoside (see 37 -> 38) required in the ring C sugar of the high mannose core. (c) 2006 Elsevier Ltd. All rights reserved.