1,5-Anhydro-3-O-acetyl-2,6-dideoxy-L-arabino-hex-1-enitol | 95475-49-3

• 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: 1,5-Anhydro-3-O-acetyl-2,6-dideoxy-L-arabino-hex-1-enitol
• 英文别名: 3-O-acetyl-L-rhamnal；L-rhamnal acetate；[(2S,3S,4S)-3-hydroxy-2-methyl-3,4-dihydro-2H-pyran-4-yl] acetate
• CAS: 95475-49-3
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: LIOHHIFSTLFWMF-GEVIPFJHSA-N

物化性质

• 沸点：
  254.7±40.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,5-Anhydro-3-O-acetyl-2,6-dideoxy-L-arabino-hex-1-enitol 在 N-碘代丁二酰亚胺 、 4 A molecular sieve 、 mercury dibromide 、 mercury(II) oxide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 4.0h， 生成 methyl 3-O-acetyl-4-O-(4-O-acetyl-2,3,6-trideoxy-3-trifluoroacetamido-α-L-lyxo-hexopyranosyl)-2,6-dideoxy-2-iodo-β-L-glucopyranoside
  参考文献：
  名称：

  含有柔红胺的蒽环类二糖苷的合成及其抗肿瘤活性。

  摘要：

  Daunosamine作为其4-O-乙酰-3-N-三氟乙酰基糖基氯衍生物（1b），已将α-L-糖苷与L-鼠李的3-和4-mono-O-乙酰基衍生物偶合，得到二糖已经评估了通过连续的烷氧基碘化-三丁基锡烷还原而转化为相应的2-脱氧糖苷的糖基衍生物。用甲基糖苷成功证明的序列已成功地以道诺霉素作为糖苷配基进行了延伸，从而为制备7-O- [3-O-（3-氨基-2,3,6-三苯氧基-α-L-lyxo-己吡喃糖基）-2,6-二脱氧-α-L-阿拉伯糖-己吡喃糖基] daunomycinone盐酸盐（15），它是一种天然的蒽环类抗生素的类似物，含有道诺糖胺和2,6-二脱氧-L-己糖。

  DOI：

  10.7164/antibiotics.46.1720
• 作为产物：
  描述：

  (3aS,4S,7aS)-2,2-dibutyl-4-methyl-4,7a-dihydro-3aH-[1,3,2]dioxastannolo[4,5-c]pyran 生成 1,5-Anhydro-3-O-acetyl-2,6-dideoxy-L-arabino-hex-1-enitol
  参考文献：
  名称：

  MEREYALA, HARI BABU;KULKARNI, VINAYAK R., CARBOHYDR. RES., 187,(1989) N, C. 154-158

  摘要：

  DOI：

文献信息

• Simple oxidation of 3-O-silylated glycals: application in deblocking 3-O-protected glycals
  作者：Andreas Kirschning、Ulrike Hary、Claus Plumeier、Monika Ries、Lars Rose

  DOI：10.1039/a807479h

  日期：——

  A high yielding allylic oxidation of 3-O-silylated glycals 5–10 with the reagent system PhI(OAc)2–TMSN3 is presented. The iodine(III) species generated under these conditions is a lot more effective for generating carbohydrate-derived 3-trialkylsiloxy-2,3-dihydro-4H-pyran-4-ones 11–15 than is [hydroxy(tosyloxy)iodo]benzene, the Koser reagent. Even disaccharide 9 containing the oxidation-labile phenylseleno group is smoothly oxidized to the corresponding enone 15. The hypervalent azido iodine reagent is complementary to the Koser reagent, because 3-O-benzylated or -acylated glycals cannot be oxidized. When the iodine(III)-mediated oxidation of 3-O-silylated or -benzylated glycals is followed by a reduction step, the formal 3-O-deblocking of glycals is achieved. In particular, the Luche reduction of enones obtained from the oxidation of lyxo-configured glycals 24 and 26 is highly selective and exclusively affords the corresponding lyxo-configured glycals 28 and 30. In some cases, these products can be transformed under Mitsunobu conditions into glycals with inverted configuration at C-3 in moderate yield.

  提出了一种高产率的3-O-硅烷化糖醇5–10的烯丙氧化反应，使用的试剂系统为PhI(OAc)2–TMSN3。在这些条件下生成的碘(III)物种相比于Koser试剂[羟基(托芳基羟基)碘]苯，更有效地生成以碳水化合物为基础的3-三烷基硅氧基-2,3-二氢-4H-吡喃-4-酮11–15。即使是含有易氧化的苯基硒基的二糖9，也能平稳地氧化成相应的烯酮15。超价的叠氮碘试剂与Koser试剂互补，因为3-O-苄基化或-酰基化的糖醇无法被氧化。当3-O-硅烷化或-苄基化的糖醇进行碘(III)介导的氧化后再进行还原步骤时，可以实现糖醇的形式性3-O-去堵功能。特别是，从lyxo构型的糖醇24和26氧化得到的烯酮进行Luche还原反应时，选择性极高，专门生成相应的lyxo构型的糖醇28和30。在某些情况下，这些产物可以在Mitsunobu条件下转化为C-3配置反转的糖醇，且产率适中。
• Efficient Synthesis of the Tetracyclic Aminoquinone Moiety of Marmycin A
  作者：Nathan Maugel、Barry B. Snider

  DOI：10.1021/ol9020496

  日期：2009.11.5

  An efficient four-step route to the tetracyclic aminoquinone moiety of marmycin A that proceeds in 41% overall yield from 5-nitronaphthoquinone and 5-methyl-1-vinylcyclohexene will facilitate preparation of marmycin A analogues for biological evaluation. The Diels-Alder reaction gave exclusively the desired adduct that is favored by steric considerations rather than the regioisomeric adduct that is favored by electronic considerations.
• Selective acylation of 6-deoxyglycals
  作者：Derek Horton、Waldemar Priebe、Oscar Varela

  DOI：10.1016/s0008-6215(00)90679-7

  日期：1985.12

  L-Rhamnal was acylated under a variety of conditions with various acylating reagents. Substitution of the hydroxyl group in the allylic position was favored when acetyl chloride, N-acetylimidazole, benzoyl chloride, and N-benzoylimidazole were used (40-60% net yields), whereas the homoallylic group of L-rhamnal was selectively protected when acetic anhydride-pyridine was employed for the acylation. The monoacetates of L-fucal underwent O-3----O-4 migration of the acetyl group, and selective acylation of this glycal could not be achieved.
• Regioselectivity in the reactivity of dibutylstannylene derivatives of glycals
  作者：Hari Babu Mereyala、Vinayak R. Kulkarni

  DOI：10.1016/0008-6215(89)80064-3

  日期：1989.4
• Selective silylation of 6-deoxyglycals
  作者：Derek Horton、Waldemar Priebe、Oscar Varela

  DOI：10.1016/s0008-6215(00)90680-3

  日期：1985.12