Acetic acid (2R,3R,4R)-4-acetoxy-2-acetoxymethyl-6-methoxy-tetrahydro-pyran-3-yl ester | 1043893-21-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid (2R,3R,4R)-4-acetoxy-2-acetoxymethyl-6-methoxy-tetrahydro-pyran-3-yl ester
• 英文别名: [(2R,3R,4R)-3,4-diacetyloxy-6-methoxyoxan-2-yl]methyl acetate
• CAS: 1043893-21-5
• 化学式: C₁₃H₂₀O₈
• 分子量: 304.297
• InChiKey: JTQYAWBAXLZBQR-ZHRBOBAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Acetic acid (2R,3R,4R)-4-acetoxy-2-acetoxymethyl-6-methoxy-tetrahydro-pyran-3-yl ester 在 4-二甲氨基吡啶 、 RhCl(PPh₃)3 吡啶 、 咪唑 、 lead(IV) acetate 、 18-冠醚-6 、 三氟化硼乙醚 、 四丁基溴化铵 、 氢气 、 sodium methylate 、 双(三甲基硅烷基)氨基钾 、 三丁基氧化锡 、 lithium bromide 作用下， 以 二氯甲烷 、 苯 为溶剂， -78.0~80.0 ℃ 、101.33 kPa 条件下， 反应 128.83h， 生成 (2R,5S)-5-Benzyloxy-6-[1,3]dithian-2-yl-2-methyl-hexanoic acid methyl ester
  参考文献：
  名称：

  Application of the Ibuka-Yamamoto reaction to a problem in stereochemical communication: a strategy for the stereospecific synthesis and stabilization of the triene substructure of rapamycin through sulfone substitution

  摘要：

  The aldehydes 49 and 55 corresponding to carbons 13-30 in a projected total synthesis of rapamycin have been synthesized. The LACDAC technology was used to elaborate dithiane enal 5. The aldehyde 4 was synthesized from D-(+)-glucose. A critical element of that construction involved cuprate-induced displacement reactions on enoates 7 and 8 (see formation of esters 9a and 9b) to correlate the stereochemistry of carbons 8 and 12. The feasibility of conducting a Nozaki-Kishi reaction between iodosulfone 6 and aldehyde 4 was a major simplification. Julia coupling between sulfone 5 and aldehyde 43 was followed by acetylation and elimination of acetic acid. The triene sulfone 54 was obtained stereospecifically. The C4 sulfone linkage is a considerable stabilizing element on the C1-C6 triene. Its presence allows for removal of the dithiane linkage (see formation of aldehyde 55). Cleavage of the sulfone is accomplished with sodium analgam without reduction of an aldehyde function at C30 (see formation of 49).

  DOI：

  10.1021/jo00020a027
• 作为产物：
  描述：

  methyl 3,4,6-tri-O-acetyl-2-deoxy-2-iodo-α-D-altropyranoside 在 potassium fluoride 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 生成 Acetic acid (2R,3R,4R)-4-acetoxy-2-acetoxymethyl-6-methoxy-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  Application of the Ibuka-Yamamoto reaction to a problem in stereochemical communication: a strategy for the stereospecific synthesis and stabilization of the triene substructure of rapamycin through sulfone substitution

  摘要：

  The aldehydes 49 and 55 corresponding to carbons 13-30 in a projected total synthesis of rapamycin have been synthesized. The LACDAC technology was used to elaborate dithiane enal 5. The aldehyde 4 was synthesized from D-(+)-glucose. A critical element of that construction involved cuprate-induced displacement reactions on enoates 7 and 8 (see formation of esters 9a and 9b) to correlate the stereochemistry of carbons 8 and 12. The feasibility of conducting a Nozaki-Kishi reaction between iodosulfone 6 and aldehyde 4 was a major simplification. Julia coupling between sulfone 5 and aldehyde 43 was followed by acetylation and elimination of acetic acid. The triene sulfone 54 was obtained stereospecifically. The C4 sulfone linkage is a considerable stabilizing element on the C1-C6 triene. Its presence allows for removal of the dithiane linkage (see formation of aldehyde 55). Cleavage of the sulfone is accomplished with sodium analgam without reduction of an aldehyde function at C30 (see formation of 49).

  DOI：

  10.1021/jo00020a027

文献信息

• Sulfonamidoglycosylation of Methyl Glycosides Employing Perchloric Acid Supported on Silica Gel
  作者：Pedro A. Colinas、Nicolás A. Núñez、Rodolfo D. Bravo

  DOI：10.1080/07328300802030829

  日期：2008.6

  The sulfonamidoglycosylation of methyl glycosides in the presence of perchloric acid immobilized on silica gel proceeded effectively to afford the corresponding sulfonamido glycosides with good to high yields with minimal workup and short reaction times. This methodology was applied to the synthesis of some N-glycosyl sulfamides, which showed low nanomolar activity against human carbonic anhydrase.