(3aS,4R,6S,7R,7aR)-7-hydroxy-6-[[(2R,3S,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-2-one | 163228-32-8

• 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: (3aS,4R,6S,7R,7aR)-7-hydroxy-6-[[(2R,3S,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-2-one
• CAS: 163228-32-8
• 化学式: C₃₆H₅₀O₁₀Si
• 分子量: 670.872
• InChiKey: KKVSKXUSJAAGRY-GJOPBLTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.27
• 重原子数：
  47
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  111
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (3aS,4R,6S,7R,7aR)-7-hydroxy-6-[[(2R,3S,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-2-one 在 四丁基氟化铵 、 四丁基溴化铵 、 sodium methylate 、 sodium hydride 、 二正丁基氧化锡 、 三丁基氧化锡 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 32.08h， 生成 (2R,3S,4S,5R,6S)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-[[(2R,3S,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]oxan-3-ol
  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
• 作为产物：
  描述：

  3,6-Di-O-苯甲基-D-葡萄醛 、 (1aS,3R,3aS,6aS,6bR)-3-Triisopropylsilanyloxymethyl-tetrahydro-1,2,4,6-tetraoxa-cyclopropa[e]inden-5-one 在 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 以86%的产率得到(3aS,4R,6S,7R,7aR)-7-hydroxy-6-[[(2R,3S,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-2-one
  参考文献：
  名称：

  Synthesis of Asialo GM₁. New Insights in the Application of Sulfonamidoglycosylation in Oligosaccharide Assembly:  Subtle Proximity Effects in the Stereochemical Governance of Glycosidation

  摘要：

  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.

  DOI：

  10.1021/ja9724957

文献信息

• Total Synthesis and Proof of Structure of a Human Breast Tumor (Globo-H) Antigen
  作者：Tae Kyo Park、In Jong Kim、Shuanghua Hu、Mark T. Bilodeau、John T. Randolph、Ohyun Kwon、Samuel J. Danishefsky

  DOI：10.1021/ja962048b

  日期：1996.1.1

  The total synthesis of the Hakomori MBr1 antigen, heavily expressed on human breast tumors, is related. The construction involved the assembly of four glycals: (17 (twice), 18, 20, and 26) and an l-fucose derivative, 34. The sensitivity of the stereochemistry of sulfonamido galactosylation by a terminal galactose ring as a function of the state of protection status of its C4 alcohol was exploited in

  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。）
• Total Synthesis of a Human Breast Tumor Associated Antigen
  作者：Mark T. Bilodeau、Tae Kyo Park、Shuanghua Hu、John T. Randolph、Samuel J. Danishefsky、Philip O. Livingston、Shengli Zhang

  DOI：10.1021/ja00134a043

  日期：1995.7
• Total Syntheses of Tumor-Related Antigens N3:  Probing the Feasibility Limits of the Glycal Assembly Method
  作者：Hyunjin M. Kim、In Jong Kim、Samuel J. Danishefsky

  DOI：10.1021/ja0022730

  日期：2001.1.1

  The total syntheses of two octasaccharide antigens isolated from human milk, 1 and 2, and their corresponding allyl glycosides, 3 and 4, have been achieved by utilizing the glycal method, Convergent assembly of the core hexasaccharides and concurrent introduction of two alpha -L-fucosyl moieties at the late stage of the syntheses provided these complex:carbohydrates in a concise manner. With synthetic material obtained, biological evaluations of these antigens as potential gastrointestinal cancer immunotherapeutic agents have been initiated.
• Application of the Glycal Assembly Method to the Concise Synthesis of Neoglycoconjugates of Ley and Leb Blood Group Determinants and of H-Type I and H-Type II Oligosaccharides
  作者：Samuel J. Danishefsky、Victor Behar、John T. Randolph、Kenneth O. Lloyd

  DOI：10.1021/ja00126a011

  日期：1995.5

  The power of the glycal assembly strategy for reaching Lewis and H-type blood group determinants is demonstrated herein. Three key elements form the basis of the method. Thus, alpha-epoxides derived from galactal cyclic carbonate 13 are produced stereospecifically and are highly effective beta-galactosyl donors. Also, 6-monoprotected glucals can be regiospecifically glycosylated at the C-3 hydroxyl (see 23 + 13 --> 24). Moreover, glycosylation via a glycal epoxide produces a unique C-2 hydroxyl in the product which can be exploited as the acceptor site for branching (see formation of 26).
• 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.