(2R,3S)-6-(allyloxy)-3-(benzyloxy)-2-((benzyloxy)methyl)-3,6-dihydro-2H-pyran | 156519-01-6

• 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: (2R,3S)-6-(allyloxy)-3-(benzyloxy)-2-((benzyloxy)methyl)-3,6-dihydro-2H-pyran
• 英文别名: allyl 4,6-di-O-benzyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside；allyl 4,6-di-O-benzyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside；(2R,3S,6S)-3-phenylmethoxy-2-(phenylmethoxymethyl)-6-prop-2-enoxy-3,6-dihydro-2H-pyran
• CAS: 156519-01-6
• 化学式: C₂₃H₂₆O₄
• 分子量: 366.457
• InChiKey: NXDOFNOEZYOUKR-ZRBLBEILSA-N

物化性质

• 沸点：
  494.4±45.0 °C(predicted)
• 密度：
  1.12±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-甲基苯磺酰溴 、 (2R,3S)-6-(allyloxy)-3-(benzyloxy)-2-((benzyloxy)methyl)-3,6-dihydro-2H-pyran 以 二氯甲烷 为溶剂， 以150 mg的产率得到(3R,3aS,4R,5R,6R,7aS)-4-bromo-3-[(4-methylphenyl)sulfonylmethyl]-5-phenylmethoxy-6-(phenylmethoxymethyl)-3,3a,4,5,6,7a-hexahydro-2H-furo[2,3-b]pyran
  参考文献：
  名称：

  Stereocontrol in radical cyclizations on sugar templates

  摘要：

  The radical cyclization of alkyl hex-2-enopyranosides provides a stereocontrolled route to fused furanopyranes. The intermediate radical is generated either via the reduction of the appropriate halide by tin hydride or via sulfonyl radical addition to allyl hex-2-enopyranosides. The two methodologies are compared with respect to diastereoselectivity. Stereocontrol is discussed on the basis of conformational preference in the transition state.

  DOI：

  10.1016/s0040-4020(01)80694-3
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 sodium hydroxide 、 三氟化硼乙醚 、 四丁基硫酸氢铵 作用下， 以 乙腈 、 叔丁醇 、 苯 为溶剂， 反应 4.0h， 生成 (2R,3S)-6-(allyloxy)-3-(benzyloxy)-2-((benzyloxy)methyl)-3,6-dihydro-2H-pyran
  参考文献：
  名称：

  Stereocontrol in radical cyclizations on sugar templates

  摘要：

  The radical cyclization of alkyl hex-2-enopyranosides provides a stereocontrolled route to fused furanopyranes. The intermediate radical is generated either via the reduction of the appropriate halide by tin hydride or via sulfonyl radical addition to allyl hex-2-enopyranosides. The two methodologies are compared with respect to diastereoselectivity. Stereocontrol is discussed on the basis of conformational preference in the transition state.

  DOI：

  10.1016/s0040-4020(01)80694-3

文献信息

• Direct Ferrier rearrangement on unactivated glycals catalyzed by indium(III) chloride
  作者：Paramathevar Nagaraj、Namakkal G. Ramesh

  DOI：10.1016/j.tetlet.2009.04.084

  日期：2009.7

  Anhydrous InCl3 has been shown to efficiently catalyze the Ferrier rearrangement by a direct allylic substitution of the hydroxyl group at C-3 position of glycals to afford the corresponding 2,3-unsaturated glycosides in high yields at ambient temperature. This methodology obviates the need for protecting and/or activating the C-3 hydroxyl group of glycals. The reaction works in equal ease with both

  已经证明无水InCl 3通过在糖基的C -3位置上的羟基的直接烯丙基取代有效地催化费列重排，从而在环境温度下以高收率提供相应的2，3-不饱和糖苷。该方法避免了保护和/或活化糖基的C -3羟基的需要。将反应工作在同样容易与两个4,6-二ö苄基d -glucal和4,6-二- ö苄基d -galactal。InCl 3的温和性使该方法与具有酸不稳定基团的糖基受体兼容。反应的普遍性已通过多种醇，酚和糖亲核试剂得到证明。
• Direct one-pot conversion of acylated carbohydrates into their alkylated derivatives under heterogeneous reaction conditions using solid NaOH and a phase transfer catalyst
  作者：Soni Kamlesh Madhusudan、Geetanjali Agnihotri、Devendra S. Negi、Anup Kumar Misra

  DOI：10.1016/j.carres.2005.03.007

  日期：2005.5

  A convenient one-pot protocol for the direct conversion of acyl-protected carbohydrates into their alkylated counterparts has been developed by using alkyl halides in the presence of solid sodium hydroxide and a phase transfer catalyst. These economically convenient, mild, two-phase reaction conditions allow the preparation of a variety of monosaccharide intermediates for use in the synthesis of complex

  通过在固体氢氧化钠和相转移催化剂存在下使用烷基卤，已经开发了一种方便的一锅法方案，用于将酰基保护的碳水化合物直接转化为其烷基化的对应物。这些经济上方便，温和的两相反应条件允许制备用于合成复杂寡糖的各种单糖中间体。
• Aluminium triflate catalysed O-glycosidation: temperature-switched selective Ferrier rearrangement or direct addition with alcohols
  作者：D. Bradley G. Williams、Sandile B. Simelane、Henok H. Kinfe

  DOI：10.1039/c2ob25540e

  日期：——

  A temperature-controlled mechanism switch between the Al(OTf)3-catalysed direct addition of alcohols or the Ferrier rearrangement reactions in some glycals is presented. The scope and limitations are investigated as are the influence of the stereochemistry and nature of the protecting groups on the glycal substrate.

  提出了在Al（OTf）3催化的醇直接添加或某些糖基中的Ferrier重排反应之间的温度控制机制切换。研究了范围和局限性以及糖基上保护基的立体化学和性质的影响。
• Ferric sulfate hydrate-catalyzed O-glycosylation using glycals with or without microwave irradiation
  作者：Guisheng Zhang、Qingfeng Liu、Lei Shi、Jiuxia Wang

  DOI：10.1016/j.tet.2007.10.097

  日期：2008.1

  O-glycosylation reaction, in which the substrates are not only peracetyl glycals but also perbenzyl glucals to afford the corresponding 2,3-unsaturated-O-glycosides via Ferrier rearrangement. The reaction of the perbenzyl glucal with various alcohols catalyzed by ferric sulfate hydrate (Fe2(SO4)3·xH2O) was successfully carried out to give 2,3-unsaturated d-O-glucosides with exclusive α-selectivity and

  我们已经开发了一种新颖的基于糖基的O-糖基化反应，其中底物不仅是过乙酰基糖基，而且是过苄基葡糖基，以通过Ferrier重排提供相应的2,3-不饱和-O-糖苷。成功地进行了苄基葡糖醛与水合硫酸铁（Fe 2（SO 4）3 · x H 2 O）催化的各种醇的反应，得到2,3-不饱和d- O-葡萄糖苷，具有独特的α-选择性和没有观察到加成产物2-脱氧己吡喃糖苷的形成。这是关于全烷基糖有效经历费勒重排而不是由路易斯酸催化的醇加成的首次报道。铁2（SO 4）3 · x H 2 O是一种有效，方便且对环境无害的多相催化剂。它具有较低的催化负荷，可回收利用，且活性没有明显降低。
• Ferric Sulphate Hydrate–Catalyzed, Microwave‐Assisted Synthesis of 2,3‐Unsaturated <i>O</i>‐Glycosides via the Ferrier Reaction
  作者：Guisheng Zhang、Qingfeng Liu

  DOI：10.1080/00397910701555402

  日期：2007.10.1