3-C-(3,4,6-tri-O-benzyl-α-D-arabino-hex-2-ulopyranosyl)propene | 184155-60-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-C-(3,4,6-tri-O-benzyl-α-D-arabino-hex-2-ulopyranosyl)propene
• 英文别名: (2R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-prop-2-enyloxan-3-one
• CAS: 184155-60-0
• 化学式: C₃₀H₃₂O₅
• 分子量: 472.581
• InChiKey: JJOOLDPCJMXIJA-XQQPTAJKSA-N

物化性质

• 沸点：
  599.6±50.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-C-(3,4,6-tri-O-benzyl-α-D-arabino-hex-2-ulopyranosyl)propene 在 吡啶 、 4-二甲氨基吡啶 、 Hoveyda-Grubbs catalyst second generation 、 三氯化硼 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 7.0h， 生成
  参考文献：
  名称：

  糖稠合双环化合物的合成；构象约束支架和有用的多功能积木

  摘要：

  我们从市售的甲基吡喃葡萄糖苷开始，采用 RCM 环化方法合成了含有高度羟基化吡喃环的稠合双环多官能化合物。在新形成的环上引入了通用的 α,β-不饱和酮基团，作为这些多官能化结构单元潜力的一个例子，通过狄尔斯-阿尔德环加成反应合成了四环化合物。

  DOI：

  10.1002/ejoc.201400028
• 作为产物：
  描述：

  acetic acid 2-allyl-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl ester 在 sodium methylate 、 乙酸酐 、 二甲基亚砜 作用下， 以 甲醇 为溶剂， 反应 26.0h， 生成 3-C-(3,4,6-tri-O-benzyl-α-D-arabino-hex-2-ulopyranosyl)propene
  参考文献：
  名称：

  Multifunctionalized α,β-cyclopentenones from C-2 and C-4-ulopyranosyl compounds: a stereospecific rearrangement initiated by base

  摘要：

  Base treatment of O-benzyl protected C-2- or C-4-ulopyranosyl compounds (4 alpha, 4 beta, and 11) by either 10% Et3N or 1% K2CO3 in MeOH initiated a beta elimination to afford alpha,beta-unsaturated C-ulopyranosyl compounds (5 alpha, 5 beta, and 12), which further rearranged in a stereocontrolled manner to multifuctionalized alpha,beta-cyclopentenones (6 and 14) in 70-80% yield. Both C-alpha- and C-beta-2-ulosides (5 alpha and 5 beta) produced the same cyclopentenone 6, indicating that a 1,2-enolate is formed prior to the cleavage of the C-5-O bond. Because 6 is racemic, it was probably formed by the intramolecular cycloaldolization of two equally populated enantiomeric intermediates. When treated with 90% Et3N in MeOH, 5 alpha yielded almost exclusively 15 (isomer of 6), which was formed by a migration of the double bond in 5 alpha during the previously described rearrangement. Thus either 6 or 15 was the major product, depending on the base used. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00187-2

文献信息

• Synthesis of 2-Deoxy-2-<i>C</i>-alkyl Glycal and Glycopyranosides from 2-Hydroxy Glycal Ester
  作者：Gour Chand Daskhan、Narayanaswamy Jayaraman

  DOI：10.1021/jo202240f

  日期：2012.3.2

  glycal ester to the corresponding 2-deoxy-2-C-alkyl glycal in a facile manner, through key reactions including (i) C-allylation at C-1, (ii) Wittig reaction, and (iii) Cope rearrangement of a 1,5-diene derivative, is reported. The α-anomer of the 1,5-diene derivative underwent Cope rearrangement to afford 2-deoxy-2-C-glycal derivative, whereas the β-anomer was found to be unreactive. Employing this sequence

  的方法，2-羟基烯糖酯转化成相应的2-脱氧-2- Ç烷基烯糖以容易的方式，通过关键反应包括：（i）C ^ -allylation在Ç -1，（ⅱ）Wittig反应，和（ iii）报道了应对1，5-二烯衍生物的重排。对1，5-二烯衍生物的α-端基异构体进行Cope重排，得到2-脱氧-2- C-糖基衍生物，而发现β-端基异构体没有反应性。使用该序列中，3,4,6-三- ø -苄基-2- ø -乙酰基-1,5-脱水- d -阿拉伯糖-己-1- enitol转化到3,4,6-三ö -苄基-2-脱氧-2- C-烷基-1,5-脱水-d -阿拉伯糖-己-1- enitol。2-脱氧-2- C-烷基糖基衍生物是制备2-脱氧-2- C-烷基糖苷的合适的糖基供体，其通过卤代糖基化和随后的脱卤作用而介导。因此由该糖基制备了许多2-还原氧基-2- C-烷基糖苷，在还原端具有糖基和非糖基部分。
• A convenient and highly stereoselective method for synthesis of octahydropyrano[3,2-b]pyrrole derivatives
  作者：Xiaofeng Ma、Qin Tang、Jun Ke、Haibo Wang、Wei Zou、Huawu Shao

  DOI：10.1016/j.carres.2012.11.016

  日期：2013.1

  The octahydropyrano[3,2-b]pyrrole derivatives are synthesized by a double reductive amination from pyranose derivatives of nono-2,5-diuloses and octos-4-uloses and various amines. The cyclization proceeded smoothly in the presence of sodium triacetoxyborohydride to produce a series of novel fused N-heterobicyclic compounds with high stereoselectivity.

  八氢吡喃并[3，2-b]吡咯衍生物是通过壬二-2，5-二糖和八辛基-吡喃糖的吡喃糖衍生物和各种胺的双还原胺化反应合成的。在三乙酰氧基硼氢化钠的存在下，环化反应顺利进行，以生产出一系列具有高立体选择性的新型稠合N-杂环双环化合物。
• New and Easy Access to C-Glycosides of Glucosamine and Mannosamine
  作者：Laura Cipolla、Luigi Lay、Francesco Nicotra

  DOI：10.1021/jo970127f

  日期：1997.9.1
• Synthesis of glyco-Fused Bicyclic Compounds; Conformationally Constrained Scaffolds and Useful Polyfunctional Building Blocks
  作者：Francisco Cardona、Giuseppe D'Orazio、Artur M. S. Silva、Francesco Nicotra、Barbara La Ferla

  DOI：10.1002/ejoc.201400028

  日期：2014.4

  fused bicyclic polyfunctional compounds containing a highly hydroxylated pyran ring starting from commercially available methyl glucopyranoside and adopting a RCM annulation approach. The versatile α,β-unsaturated ketone group was introduced on the newly formed ring and, as an example of the potential of these polyfunctionalized building blocks, a tetracyclic compound was synthesized through a Diels–Alder

  我们从市售的甲基吡喃葡萄糖苷开始，采用 RCM 环化方法合成了含有高度羟基化吡喃环的稠合双环多官能化合物。在新形成的环上引入了通用的 α,β-不饱和酮基团，作为这些多官能化结构单元潜力的一个例子，通过狄尔斯-阿尔德环加成反应合成了四环化合物。
• Multifunctionalized α,β-cyclopentenones from C-2 and C-4-ulopyranosyl compounds: a stereospecific rearrangement initiated by base
  作者：Wei Zou、Zerong Wang、Edith Lacroix、Shih-Hsiung Wu、Harold J Jennings

  DOI：10.1016/s0008-6215(01)00187-2

  日期：2001.8

  Base treatment of O-benzyl protected C-2- or C-4-ulopyranosyl compounds (4 alpha, 4 beta, and 11) by either 10% Et3N or 1% K2CO3 in MeOH initiated a beta elimination to afford alpha,beta-unsaturated C-ulopyranosyl compounds (5 alpha, 5 beta, and 12), which further rearranged in a stereocontrolled manner to multifuctionalized alpha,beta-cyclopentenones (6 and 14) in 70-80% yield. Both C-alpha- and C-beta-2-ulosides (5 alpha and 5 beta) produced the same cyclopentenone 6, indicating that a 1,2-enolate is formed prior to the cleavage of the C-5-O bond. Because 6 is racemic, it was probably formed by the intramolecular cycloaldolization of two equally populated enantiomeric intermediates. When treated with 90% Et3N in MeOH, 5 alpha yielded almost exclusively 15 (isomer of 6), which was formed by a migration of the double bond in 5 alpha during the previously described rearrangement. Thus either 6 or 15 was the major product, depending on the base used. (C) 2001 Elsevier Science Ltd. All rights reserved.