β-L-boivinose | 102850-50-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: β-L-boivinose
• 英文别名: L-lyxo-2,6-dideoxy-hexopyranose；β-L-lyxo-2,6-dideoxy-hexopyranose；2,6-Dideoxy-β-L-lyxo-hexopyranose；β-L-oliopyranose；(2S,4R,5S,6S)-6-methyloxane-2,4,5-triol
• CAS: 102850-50-0
• 化学式: C₆H₁₂O₄
• 分子量: 148.159
• InChiKey: FDWRIIDFYSUTDP-BGPJRJDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  69.9
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (1S,4S,5R,6S)-4-methyl-2-oxo-3,7-dioxabicyclo[4.1.0]heptan-5-yl acetate 在 sodium tetrahydroborate 、 二苯基二硒醚 、 sodium acetate 、 sodium cyanoborohydride 、 potassium carbonate 、 溶剂黄146 作用下， 以 甲醇 、 异丙醇 为溶剂， 反应 1.0h， 生成 β-L-boivinose
  参考文献：
  名称：

  A divergent strategy for constructing a sugar library containing 2,6-dideoxy sugars and uncommon sugars with 4-substitution

  摘要：

  A practical strategy has been developed for delivering 2,6-dideoxy sugars and uncommon sugars with 4-substitution. This strategy employed Ferrier rearrangement reaction and BF3 center dot OEt2-induced peroxidation to construct key intermediates 2,3-unsaturated glycosides and alpha,beta-unsaturated lactones from peracetyl rhamnal. After further derivatization, four uncommon sugars with 4-substitution and eight uncommon sugar units with 3,4-disubstitution were successfully synthesized. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.07.019

文献信息

• Nucleophilic Addition to 2,3-Disubstituted Butanal Derivatives and Their Application to Natural Product Synthesis
  作者：Hidekazu Horie、Hideaki Akaike、Keisuke Kato、Hiroyuki Akita

  DOI：10.1248/cpb.58.1411

  日期：——

  The reaction of 2,3-anti-2-tert-butyldimethylsiloxy-3-substituted butanal derivative [anti-B, (±)-10 and (±)-16] derived from trans-(2,3)-epoxy butanoate (1) with carbon nucleophiles [α-furyl anion, acetate anion, and indium (In)-assisted allyl anion] has been investigated to give selectively the anti-, anti-adduct D. This anti-stereoselection could be explained by the Felkin–Anh transition state model. Thus obtained anti-, anti-adducts (±)-17 and (±)-38 were formally converted to natural products, (±)-asperlin (2) and (±)-olivose (4), respectively. The major anti-, anti-adduct (±)-26 was converted to (±)-digitoxose (3), while the minor anti-, syn-adduct (±)-27 was also converted to (±)-olivose (4). The reaction of (±)-10 with tert-butyl acetate anion gave predominantly afforded the anti-, anti-adduct (±)-23, which was converted to (±)-1,5-dideoxyhexitol (25). Alternately, the reaction of 2,3-syn-2-tert-butyldimethylsiloxy-3-p-methoxyphenoxy butanal derivative [syn-B, (±)-14] derived from trans-(2,3)-epoxy butanoate (1) with carbon nucleophile (In-assisted allyl anion) afforded a ca. 1 : 1 mixture of the syn-, anti-adduct E [(±)-32 or (±)-34] and syn-, syn-adduct F [(±)-33 or (±)-35]. After separation of this mixture, (±)-34 and (±)-35 were separately converted to (±)-oliose (5) and (±)-boivinose (6), respectively.

  2,3-抗-2-叔丁基二甲基硅氧基-3-取代的丁醛衍生物[抗-B,(±)-10和(±)-16]衍生自反式-(2,3)-环氧丁酸酯的反应( 1）与碳亲核试剂[α-呋喃基阴离子、乙酸根阴离子和铟（In）辅助的烯丙基阴离子]进行了研究，以选择性地产生反加合物D。这种反立体选择可以通过Felkin- Anh 过渡状态模型。由此获得的抗-、抗加合物(±)-17和(±)-38分别正式转化为天然产物(±)-asperlin(2)和(±)-olivose(4)。主要的抗、抗加合物 (±)-26 转化为 (±)-洋地黄糖 (3)，而次要的抗、顺加合物 (±)-27 也转化为 (±)-橄榄糖 (4) ）。 (±)-10与乙酸叔丁酯阴离子的反应主要产生反加合物(±)-23，其转化为(±)-1,5-二脱氧己糖醇(25)。或者，由反式-(2,3)-环氧丁酸酯衍生的2,3-syn-2-叔丁基二甲基硅氧基-3-对甲氧基苯氧基丁醛衍生物[syn-B, (±)-14]的反应 (1)与碳亲核试剂（In辅助烯丙基阴离子）提供约。顺式、反式加合物E[(±)-32或(±)-34]和顺式、顺式加合物F[(±)-33或(±)-35]的1:1混合物。分离该混合物后，(±)-34和(±)-35分别转化为(±)-寡糖(5)和(±)-牛维糖(6)。