benzyl 2-O-p-tosyl-3,4-dideoxy-α-D-glycero-pent-3-enopyranoside | 160977-64-0

• 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: benzyl 2-O-p-tosyl-3,4-dideoxy-α-D-glycero-pent-3-enopyranoside
• 英文别名: [(2R,3R)-2-phenylmethoxy-3,6-dihydro-2H-pyran-3-yl] 4-methylbenzenesulfonate
• CAS: 160977-64-0
• 化学式: C₁₉H₂₀O₅S
• 分子量: 360.431
• InChiKey: OIDAXJSROQQHLA-RTBURBONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  70.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  benzyl 2-O-p-tosyl-3,4-dideoxy-α-D-glycero-pent-3-enopyranoside 在 四(三苯基膦)钯 、 sodium hydride 、 二甲基亚砜 、 三苯基膦 作用下， 反应 27.33h， 生成 benzyl 2,3,4-trideoxyribopyranosido<4,3,2-cd>-10,10-bis(methoxycarbonyl)bicyclo<3.3.0>octan-7-en-6-one
  参考文献：
  名称：

  Palladium−Cobalt-Mediated Double Annulation Process:  A New Strategy to Chiral and Polysubstituted Bis-Cyclopentanoids on Carbohydrate Precursors

  摘要：

  The iodohydrins 2, 4, and 5 mere prepared by the ring opening of benzyl 2-O-p-tosyl-3,4-anhydro-beta-L-arabinopyranoside (1) or benzyl 2,3-anhydro-4-O-acetyl-alpha-D-ribopyranoside (3), respectively, using sodium acetate, sodium iodide, and acetic acid in acetone which on treatment with POCl3 in pyridine yielded the unsaturated sugars 6 and 7. After deacetylation of 7 with MeOH/H2O/Et(3)N (3:2:1) and treatment of 8 with tosyl chloride/pyridine at 50 degrees C 9 was obtained. The reaction of benzyl 2-O-p-tosyl-3,4-dideoxy-alpha-D-glycero-pent-3-eopyranoside (6) and benzyl 2,3,4-trideoxy-4-chloro-beta-L-glycero-pent-2-enopyranoside (9) with the sodium enolate of dimethyl propargylmalonate in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0) afforded the branched-chain sugars 10 and 11. The isomer 10 was obtained as a minor product from 6 with retention of configuration around C-2, and the major isomer 11 as a result of allylic rearrangement in a ratio of 1:9. On the other hand, compound 9 afforded 10 as a major product and its regioisomer 11 as a minor product in a ratio of 8:2; formation of the above mentioned isomeric mixture involves cis and trans diastereomeric intermediates during the reaction. Treatment of these precursors with Co-2(CO)(8) in benzene followed by oxidative decomplexation with DMSO yielded in a stereoselective manner the polysubstituted bis-cyclopentanoids 12 and 13. The stereochemistry of 13 was assigned with the help of X-ray analysis. Attempts were made to prepare the tetracyclic systems 15 and 17 using 12 and 13 with 3-acetoxy-2-[(trimethylsilyl)methyl]-1-propene (14); however, the alkylation products 16 and 18 were obtained.

  DOI：

  10.1021/jo951298s
• 作为产物：
  描述：

  Benzyl-3,4-anhydro-2-O-p-tosyl-β-L-arabinopyranosid 在 吡啶 、 sodium acetate 、 溶剂黄146 、 sodium iodide 、 三氯氧磷 作用下， 以 丙酮 为溶剂， 反应 4.0h， 生成 benzyl 2-O-p-tosyl-3,4-dideoxy-α-D-glycero-pent-3-enopyranoside
  参考文献：
  名称：

  Palladium−Cobalt-Mediated Double Annulation Process:  A New Strategy to Chiral and Polysubstituted Bis-Cyclopentanoids on Carbohydrate Precursors

  摘要：

  The iodohydrins 2, 4, and 5 mere prepared by the ring opening of benzyl 2-O-p-tosyl-3,4-anhydro-beta-L-arabinopyranoside (1) or benzyl 2,3-anhydro-4-O-acetyl-alpha-D-ribopyranoside (3), respectively, using sodium acetate, sodium iodide, and acetic acid in acetone which on treatment with POCl3 in pyridine yielded the unsaturated sugars 6 and 7. After deacetylation of 7 with MeOH/H2O/Et(3)N (3:2:1) and treatment of 8 with tosyl chloride/pyridine at 50 degrees C 9 was obtained. The reaction of benzyl 2-O-p-tosyl-3,4-dideoxy-alpha-D-glycero-pent-3-eopyranoside (6) and benzyl 2,3,4-trideoxy-4-chloro-beta-L-glycero-pent-2-enopyranoside (9) with the sodium enolate of dimethyl propargylmalonate in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0) afforded the branched-chain sugars 10 and 11. The isomer 10 was obtained as a minor product from 6 with retention of configuration around C-2, and the major isomer 11 as a result of allylic rearrangement in a ratio of 1:9. On the other hand, compound 9 afforded 10 as a major product and its regioisomer 11 as a minor product in a ratio of 8:2; formation of the above mentioned isomeric mixture involves cis and trans diastereomeric intermediates during the reaction. Treatment of these precursors with Co-2(CO)(8) in benzene followed by oxidative decomplexation with DMSO yielded in a stereoselective manner the polysubstituted bis-cyclopentanoids 12 and 13. The stereochemistry of 13 was assigned with the help of X-ray analysis. Attempts were made to prepare the tetracyclic systems 15 and 17 using 12 and 13 with 3-acetoxy-2-[(trimethylsilyl)methyl]-1-propene (14); however, the alkylation products 16 and 18 were obtained.

  DOI：

  10.1021/jo951298s

文献信息

• Synthesis of polyfunctionalized bis-annulated pyranosides: Useful intermediates for triquinane synthesis
  作者：Noshena Naz、Taleb H. Al-Tel、Yousef Al-Abed、Wolfgang Voelter

  DOI：10.1016/s0040-4039(00)78441-3

  日期：1994.11

  A mild method for the synthesis of bis-cyclopentanoids on carbohydrate templates using the Pauson-Khand reaction is described.

  描述了使用Pauson-Khand反应在碳水化合物模板上合成双环戊烷类化合物的温和方法。
• Carbohydrates to Pyrano-Furanoids: New and Regioselective Palladium-Catalyzed Syntheses of Tetrasubstituted Furanoids from Carbohydrate Scaffolds
  作者：Taleb H. Al-Tel

  DOI：10.1515/znb-2000-0713

  日期：2000.7.1

  A new strategy for the asymmetric syntheses of polysubstituted pyrano-furanoids using allylic sulfates derived from carbohydrate precursors and the dianion of diethoxycarbonyl acetone, catalyzed by Pd(0), is described.

  摘要 本文描述了一种使用糖类前体衍生的烯丙基硫酸盐和二乙氧基羰基丙酮的二阴离子，在Pd（0）催化下，对多取代吡喃呋喃类化合物进行不对称合成的新策略。
• Palladium−Cobalt-Mediated Double Annulation Process:  A New Strategy to Chiral and Polysubstituted Bis-Cyclopentanoids on Carbohydrate Precursors
  作者：Noshena Naz、Taleb H. Al-Tel、Yousef Al-Abed, and、Wolfgang Voelter、Robert Ficker、Wolfgang Hiller

  DOI：10.1021/jo951298s

  日期：1996.1.1

  The iodohydrins 2, 4, and 5 mere prepared by the ring opening of benzyl 2-O-p-tosyl-3,4-anhydro-beta-L-arabinopyranoside (1) or benzyl 2,3-anhydro-4-O-acetyl-alpha-D-ribopyranoside (3), respectively, using sodium acetate, sodium iodide, and acetic acid in acetone which on treatment with POCl3 in pyridine yielded the unsaturated sugars 6 and 7. After deacetylation of 7 with MeOH/H2O/Et(3)N (3:2:1) and treatment of 8 with tosyl chloride/pyridine at 50 degrees C 9 was obtained. The reaction of benzyl 2-O-p-tosyl-3,4-dideoxy-alpha-D-glycero-pent-3-eopyranoside (6) and benzyl 2,3,4-trideoxy-4-chloro-beta-L-glycero-pent-2-enopyranoside (9) with the sodium enolate of dimethyl propargylmalonate in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0) afforded the branched-chain sugars 10 and 11. The isomer 10 was obtained as a minor product from 6 with retention of configuration around C-2, and the major isomer 11 as a result of allylic rearrangement in a ratio of 1:9. On the other hand, compound 9 afforded 10 as a major product and its regioisomer 11 as a minor product in a ratio of 8:2; formation of the above mentioned isomeric mixture involves cis and trans diastereomeric intermediates during the reaction. Treatment of these precursors with Co-2(CO)(8) in benzene followed by oxidative decomplexation with DMSO yielded in a stereoselective manner the polysubstituted bis-cyclopentanoids 12 and 13. The stereochemistry of 13 was assigned with the help of X-ray analysis. Attempts were made to prepare the tetracyclic systems 15 and 17 using 12 and 13 with 3-acetoxy-2-[(trimethylsilyl)methyl]-1-propene (14); however, the alkylation products 16 and 18 were obtained.