2-deoxy-2-selenophenyl-3,4,6-tri-O-benzyl-α-glucopyranose | 122194-14-3

• 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: 2-deoxy-2-selenophenyl-3,4,6-tri-O-benzyl-α-glucopyranose
• 英文别名: (2S,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-3-phenylselanyloxan-2-ol
• CAS: 122194-14-3
• 化学式: C₃₃H₃₄O₅Se
• 分子量: 589.59
• InChiKey: SDNPHSALSFJRIE-AALIFHQRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-deoxy-2-selenophenyl-3,4,6-tri-O-benzyl-α-glucopyranose 在 4 Angstroem MS 、 三正丁基氢锡 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 甲苯 、 苯 为溶剂， 反应 8.5h， 生成 1-O-isobutyryl-2-deoxy-3,4,6-tri-O-benzyl-β-glucopyranose
  参考文献：
  名称：

  A survey of the nature of glucose acylation reactions in plant extracts

  摘要：

  A variety of plant species have been shown to catalyse anomeric acyl exchange from a number of 1-O-fatty-acyl-beta-glucoses as donor substrates to [(14)C]-glucose as an acceptor. The activity in wild tomato Lycopersicon penneliii has been analysed in detail by using analogs of glucose as accepters and a number of 1-O-acyl-beta-glucoses and 1-O-acyl-2-deoxyglucoses as acyl donors. Compared to 1-O-isobutyryl-beta-glucose, the analogous 1-O-isobutyryl-beta-2-deoxyglucose is an effective donor both to glucose (ca. 75%) and to 2-deoxyglucose (ca. 95%). On the contrary, compared to 1-O-isobutyryl-beta-glucose, 1-O-isobutyryl-alpha-2-deoxyglucose is a poor donor both to glucose (ca. 4%) and to deoxyglucose (ca. 6%). The glucose analogs free at the anomeric center such as 3-O-methylglucose and 2-deoxyglucose are competent acyl accepters from various 1-O-acyl-beta-glucoses whereas 1-O-methylglucose is not. The primary initial product of acyl transfer from 1-O-isobutyryl-beta-glucose to [(14)C]-glucose is beta-glucosidase-cleavable 1-O-acyl-[(14)C]-beta-glucose, whereas the isobutyryl-[(14)C]-3-O-methylglucose generated from 1-O-isobutyryl-beta-glucose and [(14)C]-3-O-methylglucose is beta-glucosidase-resistant. The transfer of the acyl group to 3-O-methylglucose occurs at the anomeric center; therefore the resistance to beta-glucosidase reflects the strict specificity of beta-glucosidase for glucose. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0031-9422(99)00319-2
• 作为产物：
  描述：

  (2R,3R,4S,5R)-3,4-Bis-benzyloxy-2-benzyloxymethyl-6-chloro-5-phenylselanyl-tetrahydro-pyran 在 sodium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 4.0h， 生成 2-deoxy-2-selenophenyl-3,4,6-tri-O-benzyl-α-glucopyranose
  参考文献：
  名称：

  A survey of the nature of glucose acylation reactions in plant extracts

  摘要：

  A variety of plant species have been shown to catalyse anomeric acyl exchange from a number of 1-O-fatty-acyl-beta-glucoses as donor substrates to [(14)C]-glucose as an acceptor. The activity in wild tomato Lycopersicon penneliii has been analysed in detail by using analogs of glucose as accepters and a number of 1-O-acyl-beta-glucoses and 1-O-acyl-2-deoxyglucoses as acyl donors. Compared to 1-O-isobutyryl-beta-glucose, the analogous 1-O-isobutyryl-beta-2-deoxyglucose is an effective donor both to glucose (ca. 75%) and to 2-deoxyglucose (ca. 95%). On the contrary, compared to 1-O-isobutyryl-beta-glucose, 1-O-isobutyryl-alpha-2-deoxyglucose is a poor donor both to glucose (ca. 4%) and to deoxyglucose (ca. 6%). The glucose analogs free at the anomeric center such as 3-O-methylglucose and 2-deoxyglucose are competent acyl accepters from various 1-O-acyl-beta-glucoses whereas 1-O-methylglucose is not. The primary initial product of acyl transfer from 1-O-isobutyryl-beta-glucose to [(14)C]-glucose is beta-glucosidase-cleavable 1-O-acyl-[(14)C]-beta-glucose, whereas the isobutyryl-[(14)C]-3-O-methylglucose generated from 1-O-isobutyryl-beta-glucose and [(14)C]-3-O-methylglucose is beta-glucosidase-resistant. The transfer of the acyl group to 3-O-methylglucose occurs at the anomeric center; therefore the resistance to beta-glucosidase reflects the strict specificity of beta-glucosidase for glucose. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0031-9422(99)00319-2

文献信息

• Oxidative ring contraction of benzeneselenenate adducts of glycal ethers. synthesis of showdomycin analogues
  作者：Andrew Kaye、Stephen Neidle、Colin B. Reese

  DOI：10.1016/0040-4039(88)85267-5

  日期：——

  then with water and triethylamine gave () in 67% yield; the latter compound was treated with m-chloroperbenzoic acid and the putative ring-contracted aldehyde () obtained was converted into the showdomycin analogue () in satisfactory overall yield. 3,4,6-Tri-O-benzyl--galactal () was similarly converted into the corresponding α--lyxoside ().

  首先用苯硒烯基氯，然后用水和三乙胺处理3,4,6-三-O-苄基-葡萄糖醛（），收率（％）为（）。后者化合物的溶液用米氯过苯甲酸和推定的环收缩醛（）中获得转化成showdomycin类似物（在令人满意的总收率）。3,4,6-三- Ö苄基-galactal（ ）进行类似转化成相应的α- -lyxoside（ ）。
• Studies on the Synthesis of Aureolic Acid Antibiotics: Highly Stereoselective Synthesis of Aryl 2-Deoxy-.beta.-glycosides via the Mitsunobu Reaction and Synthesis of the Olivomycin A-B Disaccharide
  作者：William R. Roush、Xiao-Fa Lin

  DOI：10.1021/ja00113a013

  日期：1995.3

  The Mitsunobu reaction of phenols and 1,2-cis-2-thiophenyl-alpha-D-glycopyranoses or 1,2-cis-2-selenophenyl-alpha-D-glycopyranoses is a very effective method for the highly stereoselective synthesis of aryl 2-deoxy-beta-D-glycosides. The equatorial 2-thiophenyl or 2-selenophenyl- substituents are easily removed by Bu(3)SnH reduction following the glycosidation reaction to provide the aryl 2-deoxy-beta-D-glycosides in good to excellent yield. The aryl beta-D-glycosides are obtained with 6.5:1 selectivity in the least selective case(Table 1) and up to >20:1 selectivity in others. The reaction appears to be S-N(2)-like in character (see 30), in that the beta:alpha reaction stereoselectivity correlates well with the alpha:beta anomeric composition of the pyranose starting material. The equatorial 2-thiophenyl or 2-selenophenyl substituents play an important role by increasing the alpha:beta anomer ratio of the pyranose starting materials. The reactions do not appear to proceed by way of free oxonium ions such as 17, since several reactions in which 17 was deliberately generated (e.g., TMS-OTf promoted reactions of glycosyl acetate 14, BF3 . Et(2)O catalyzed reactions of imidate 15) gave at best 1:1 mixtures of alpha- and beta-glycosides, and in several cases gave alpha-glycosides with >10:1 selectivity. These data also rule out the involvement of episulfonium ion 18 as a kinetically significant intermediate in reactions that proceed by way of oxonium ion 17. A short and highly effective synthesis of reducing disaccharide 53 from D-fucal was developed. This functionalized disaccharide readily undergoes Mitsunobu glycosidation with 2-naphthol, providing the model naphthyl A-B disaccharide 5 with 11:1 beta,alpha:alpha,alpha selectivity. Finally, olivin precursor 63 has also been glycosylated with 53, providing the advanced synthetic intermediate 6 with excellent diastereoselectivity.
• KAYE, ANDREW;REESE, COLIN B.;NEIDLE, STEPHEN, NUCLEOSIDES AND NUCLEOTIDES, 7,(1988) N-6, C. 609-612
  作者：KAYE, ANDREW、REESE, COLIN B.、NEIDLE, STEPHEN

  DOI：——

  日期：——
• KAYE, ANDREW;NEIDLE, STEPHEN;REESE, COLIN B., TETRAHEDRON LETT., 29,(1988) N 22, C. 2711-2714
  作者：KAYE, ANDREW、NEIDLE, STEPHEN、REESE, COLIN B.

  DOI：——

  日期：——