2,3,6-Trideoxy-4-O-p-nitrobenzoyl-3-trifluoroacetamido-L-lyxo-hexopyranose

• 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: 2,3,6-Trideoxy-4-O-p-nitrobenzoyl-3-trifluoroacetamido-L-lyxo-hexopyranose
• 英文别名: [(2S,3S,4S)-6-hydroxy-2-methyl-4-[(2,2,2-trifluoroacetyl)amino]oxan-3-yl] 4-nitrobenzoate
• 化学式: C₁₅H₁₅F₃N₂O₇
• 分子量: 392.289
• InChiKey: QHCSFALVHQYUSY-FLNMUGAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  131
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,6-Trideoxy-4-O-p-nitrobenzoyl-3-trifluoroacetamido-L-lyxo-hexopyranose 在 ammonium cerium(IV) nitrate 、 4 A molecular sieve 、 碳酸氢钠 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 38.08h， 生成 [(2S,3S,4S,6S)-6-[[(1R,3S)-3-acetyl-6-hydroxy-5,12-dioxo-3,4-dihydro-1H-naphtho[2,3-g]isochromen-1-yl]oxy]-2-methyl-4-[(2,2,2-trifluoroacetyl)amino]oxan-3-yl] 4-nitrobenzoate
  参考文献：
  名称：

  DDQ-Induced, Anomeric Specific, and Diastereoselective Benzylic Glycosidation: A Novel Approach to Heterocyclic Anthracycline Antibiotics

  摘要：

  A novel and efficient method for the oxidative glycosidation at the heterosubstituted benzylic positions with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) is described. The reaction is stereospecific with 3-substituted isochromans and isothiochroman, as well as diastereoselective with non-3-substituted isochromans. The glycosidation with a mixture of alpha- and beta-anomeric free sugars gives alpha-glycosides with absolute stereochemical control on the anomeric center. The synthetic utility of this novel methodology is demonstrated by a short, efficient, and stereoselective total synthesis of heteroanthracycline antitumor reagents.

  DOI：

  10.1021/jo00096a032
• 作为产物：
  描述：

  Methyl 2,3,6-trideoxy-4-O-p-nitrobenzoyl-3-trifluoroacetamido-α-L-lyxo-hexopyranoside 在 三氟乙酸 作用下， 反应 0.17h， 生成 2,3,6-Trideoxy-4-O-p-nitrobenzoyl-3-trifluoroacetamido-L-lyxo-hexopyranose
  参考文献：
  名称：

  Semisynthetic ε-(iso)rhodomycins: a new glycosylation variant and modification reactions

  摘要：

  Synthesis of 7-O-(3-amino-2,3,6-trideoxy-alpha-L-lyxo-hexopyranosyl)-e-(iso)rhodomycinones 16 and 17, and their 3'-morpholino derivatives are described. Glycosylation (trimethylsilyl triflate, 10:1 dichloro-methane-acetone, -35-degrees-) of 1-O-tert-butyldimethylsilyl-2,3,6-trideoxy-4-O-p-nitrobenzoyl-?? 3-trifluorace-tamido-beta-L-lyxo-hexopyranose (4) with e-rhodomycinone (e-RMN, 5) or e-isorhodomycinone (e-isoRMN, 6) afforded 7-O-alpha-glycosyl-e-RMN (9) and -e-isoRMN (12) in high yield. The glycosyl donors 2,3,6-trideoxy-4-O-p-nitrobenzoly-3-trifluoroacetamido-L-lyxo-hexopyranose (2) or its 1-O-trimethylsilylated alpha-anomer 3 were less suitable for the glycosylation of these aglycons. Saponification of 9 and 12 provided 16 and 17, respectively, which reacted with various 2,2'-oxydiacetaldehydes under conditions of reductive alkylation to give 3'-morpholinyl-e-(iso)rhodomycins.

  DOI：

  10.1016/0008-6215(91)80147-f

文献信息

• KOLAR, CENEK;KNEISSL, GUNTHER;KNODLER, URSULA;DEHMEL, KONRAD, CARBOHYDR. RES., 209,(1991) C. 89-100
  作者：KOLAR, CENEK、KNEISSL, GUNTHER、KNODLER, URSULA、DEHMEL, KONRAD

  DOI：——

  日期：——
• UMEZAWA, HAMAO;TAKEUCHI, TOMIO;NAGANAWA, HIROSHI;TATSUTA, KUNIAKI
  作者：UMEZAWA, HAMAO、TAKEUCHI, TOMIO、NAGANAWA, HIROSHI、TATSUTA, KUNIAKI

  DOI：——

  日期：——
• DDQ-Induced, Anomeric Specific, and Diastereoselective Benzylic Glycosidation: A Novel Approach to Heterocyclic Anthracycline Antibiotics
  作者：Yao-Chang Xu、Elaine Lebeau、Giorgio Attardo、Peter L. Myers、John W. Gillard

  DOI：10.1021/jo00096a032

  日期：1994.8

  A novel and efficient method for the oxidative glycosidation at the heterosubstituted benzylic positions with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) is described. The reaction is stereospecific with 3-substituted isochromans and isothiochroman, as well as diastereoselective with non-3-substituted isochromans. The glycosidation with a mixture of alpha- and beta-anomeric free sugars gives alpha-glycosides with absolute stereochemical control on the anomeric center. The synthetic utility of this novel methodology is demonstrated by a short, efficient, and stereoselective total synthesis of heteroanthracycline antitumor reagents.
• Semisynthetic ε-(iso)rhodomycins: a new glycosylation variant and modification reactions
  作者：Cenek Kolar、Günther Kneissl、Ursula Knödler、Konrad Dehmel

  DOI：10.1016/0008-6215(91)80147-f

  日期：1991.1

  Synthesis of 7-O-(3-amino-2,3,6-trideoxy-alpha-L-lyxo-hexopyranosyl)-e-(iso)rhodomycinones 16 and 17, and their 3'-morpholino derivatives are described. Glycosylation (trimethylsilyl triflate, 10:1 dichloro-methane-acetone, -35-degrees-) of 1-O-tert-butyldimethylsilyl-2,3,6-trideoxy-4-O-p-nitrobenzoyl-?? 3-trifluorace-tamido-beta-L-lyxo-hexopyranose (4) with e-rhodomycinone (e-RMN, 5) or e-isorhodomycinone (e-isoRMN, 6) afforded 7-O-alpha-glycosyl-e-RMN (9) and -e-isoRMN (12) in high yield. The glycosyl donors 2,3,6-trideoxy-4-O-p-nitrobenzoly-3-trifluoroacetamido-L-lyxo-hexopyranose (2) or its 1-O-trimethylsilylated alpha-anomer 3 were less suitable for the glycosylation of these aglycons. Saponification of 9 and 12 provided 16 and 17, respectively, which reacted with various 2,2'-oxydiacetaldehydes under conditions of reductive alkylation to give 3'-morpholinyl-e-(iso)rhodomycins.