Toluene-4-sulfonic acid (2S,3R,4R,5R)-2-benzyloxy-4-hydroxy-5-iodo-tetrahydro-pyran-3-yl ester | 176504-81-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Toluene-4-sulfonic acid (2S,3R,4R,5R)-2-benzyloxy-4-hydroxy-5-iodo-tetrahydro-pyran-3-yl ester
• CAS: 176504-81-7
• 化学式: C₁₉H₂₁IO₆S
• 分子量: 504.343
• InChiKey: VGLICQOQCMYDEY-HCXYKTFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  82.06
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Toluene-4-sulfonic acid (2S,3R,4R,5R)-2-benzyloxy-4-hydroxy-5-iodo-tetrahydro-pyran-3-yl ester 在 吡啶 、 四(三苯基膦)钯 、 sodium hydride 、 二甲基亚砜 、 三苯基膦 、 三氯氧磷 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 sodium acetate 、 溶剂黄146 、 sodium iodide 作用下， 以 丙酮 为溶剂， 以95%的产率得到Toluene-4-sulfonic acid (2S,3R,4R,5R)-2-benzyloxy-4-hydroxy-5-iodo-tetrahydro-pyran-3-yl ester
  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