di-O-(trimethylacetyl)-D-xylal | 172488-65-2

• 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: di-O-(trimethylacetyl)-D-xylal
• 英文别名: 3,4-di-O-pivaloyl-D-xylal；tri-O-pivaloyl-D-xylal；xylal dipivaloate；[(3R,4R)-4-(2,2-dimethylpropanoyloxy)-3,4-dihydro-2H-pyran-3-yl] 2,2-dimethylpropanoate
• CAS: 172488-65-2
• 化学式: C₁₅H₂₄O₅
• 分子量: 284.353
• InChiKey: ZDJNZWFCTDIAGD-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  di-O-(trimethylacetyl)-D-xylal 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 2,2-Dimethyl-propionic acid (E)-(S)-1-(2,2-dimethyl-propionyloxymethyl)-3-(4aS,6S,9aR)-4a,6,9,9a-tetrahydro-2H-1,5-dioxa-benzocyclohepten-6-yl-allyl ester
  参考文献：
  名称：

  Ciguatoxin和Gambiertoxin 4b左端的镜像合成。

  摘要：

  已经以对映体形式合成了与西瓜毒素和冈比亚毒素4b的AB片段有关的三种化合物和西瓜毒素的ABC片段的两个非对映异构体（在C-2位置）。从相应的戊糖衍生物中选择性引入C-2位的立体化学。通过对乙炔双（钴六羰基）配合物进行尼古拉斯（Nicholas）型环化，然后进行还原性解配合，完成具有侧链的A环的构建。

  DOI：

  10.1021/jo980088n
• 作为产物：
  描述：

  3,4-二-乙酰基-D-木糖烯 在 4-二甲氨基吡啶 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 di-O-(trimethylacetyl)-D-xylal
  参考文献：
  名称：

  Ciguatoxin和Gambiertoxin 4b左端的镜像合成。

  摘要：

  已经以对映体形式合成了与西瓜毒素和冈比亚毒素4b的AB片段有关的三种化合物和西瓜毒素的ABC片段的两个非对映异构体（在C-2位置）。从相应的戊糖衍生物中选择性引入C-2位的立体化学。通过对乙炔双（钴六羰基）配合物进行尼古拉斯（Nicholas）型环化，然后进行还原性解配合，完成具有侧链的A环的构建。

  DOI：

  10.1021/jo980088n

文献信息

• Highly stereoselective addition of organozinc reagents to pentopyranose derived glycals: effect of protecting group and assignment of C-glycoside stereochemistry
  作者：Matthew J Cook、Matthew J.E Fletcher、Diane Gray、Peter J Lovell、Timothy Gallagher

  DOI：10.1016/j.tet.2004.04.004

  日期：2004.5

  The nucleophilic addition of ethyl 3-propionylzinc iodide to a variety of differently protected pentopyranose derived d-glycals 6a–g proceeds with good to high levels of diastereoselectivity to provide the corresponding β-C-glycosides 7. The stereochemistry of the para-nitrobenzoate derivative 7d has been confirmed by X-ray crystallography, and the stereochemistry of the other β-C-glycoside products

  将3-丙酰碘化乙基乙酯亲核加成到各种受不同保护的戊吡喃糖衍生的d-糖6a - g上，具有很好的非对映选择性，提供了相应的β- C-糖苷7。所述的立体化学对-nitrobenzoate衍生物7D已通过X射线晶体学确认，其它β-的立体化学Ç糖苷产品已关联到7d的。观察到的立体化学结果支持了Isobe的早期建议，即通空效应对于稳定和控制11代表的中间氧鎓物种的反应性很重要。
• Partial synthesis of ciguatoxin (5R)-ABC segment
  作者：Rungnapha Saeeng、Minoru Isobe

  DOI：10.1016/s0040-4039(99)00041-6

  日期：1999.3

  An ABC segment of ciguatoxin has been synthesized in a correct enantiomeric form from a D-glucose derivative based on the route for the opposite enantiomer by switching enantiomerism of a pseudosymmetric intermediate. This route, however, has been improved in several steps and ended up with a vinylthioether group for future extension toward the D ring of ciguatoxin molecule. (C) 1999 Elsevier Science Ltd. All rights reserved.
• 1,4-anti induction in C-glycosylation of pentose glycals
  作者：Seijiro Hosokawa、Bettina Kirschbaum、Minoru Isobe

  DOI：10.1016/s0040-4039(98)00047-1

  日期：1998.4

  The C-glycosylation of pentose glycals with silylacetylenes or allylsilanes via oxocarbenium ion intermediates proceeded under high regio-and stereoselectivity giving the 1,4-anti products as the predominant products. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Saeeng, Rungnapha; Isobe, Minoru, Heterocycles, 2001, vol. 54, # 2, p. 789 - 798
  作者：Saeeng, Rungnapha、Isobe, Minoru

  DOI：——

  日期：——
• Chlorodifluoromethyl-substituted monosaccharide derivatives—radical activation of the carbon–chlorine-bond
  作者：Anita Wegert、Martin Hein、Helmut Reinke、Norbert Hoffmann、Ralf Miethchen

  DOI：10.1016/j.carres.2006.08.023

  日期：2006.11

  The dithionite-mediated addition of BrCF2Cl to 3,4-di-O-pivaloyl-D-xylal (1) generated preferably 1-CF2Cl-substituted products, that is, (2-bromo-2-deoxy-3,4-di-O-pivaloyl-beta-D-xylopyranosyl)-chlorodifluoromethane and (2-deoxy-3,4-di-O-pivaloyl-beta-D-threo-pentopyranosyl)-chlorodifluoromethane. Selected chlorodifluorornethyl-substituted monosaccharide derivatives were hydrodechlorinated or alkylated at the CF2Cl-group using tin reagents under radical reaction conditions. Thus, hydrodechlorinations of (2,3,4-tri-O-acetyl-6-deoxy-alpha-L-gal actopyranosyl)-chlorodifluoromethane and of methyl 3,4-di-O-acetyl-2-C-chlorodifluoromethyl-2,6-dideoxy-alpha/beta-L-glucopyranoside are reported using tri-n-butyltin hydride initiated by AIBN. UV-initiated allylations are reported for reactions of (2-deoxy-3,4-di-O-pivaloyl-beta-D-threo-pentopyranosyl)-chlorodifluoromethane, (2,3,4-tri-O-acetyl-6-deoxy-alpha-L-galactopyranosyl)-chlorodifluoromethane, 1,3,4,6-tetra-O-acetyl-2-C-chlorodifluoromethyl-2-deoxy-alpha-D-glucopyranose, 1,3,4,6-tetra-O-acetyl-2-C-chlorodifluoromethyl-2-deoxy-alpha-D-mannopyranose and methyl 3,4-di-O-acetyl-2-C-chlorodifluoromethyl-2-deoxy-alpha/beta-D-rabinopyranoside with allyltri-n-butyltin. (c) 2006 Elsevier Ltd. All rights reserved.