Methanesulfonic acid (2R,3S,4R)-4-benzyloxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-3,4-dihydro-2H-pyran-3-yl ester | 135663-44-4

• 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: Methanesulfonic acid (2R,3S,4R)-4-benzyloxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-3,4-dihydro-2H-pyran-3-yl ester
• 英文别名: [(2R,3S,4R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-phenylmethoxy-3,4-dihydro-2H-pyran-3-yl] methanesulfonate
• CAS: 135663-44-4
• 化学式: C₂₀H₃₂O₆SSi
• 分子量: 428.622
• InChiKey: WOYZSKFPKWBVMJ-QRVBRYPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Methanesulfonic acid (2R,3S,4R)-4-benzyloxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-3,4-dihydro-2H-pyran-3-yl ester 在 RhCl(PPh₃)3 吡啶 、 咪唑 、 chromium dichloride 、 lead(IV) acetate 、 4-二甲氨基吡啶 、 potassium fluoride 、 potassium dihydrogenphosphate 、 sodium amalgam 、 N-氯代丁二酰亚胺 、 N-溴代丁二酰亚胺(NBS) 、 N-碘代丁二酰亚胺 、 锂硼氢 、 正丁基锂 、 2,6-二叔丁基吡啶 、 cerium(III) chloride 、 偶氮二异丁腈 、 三氟化硼乙醚 、 氢气 、 三正丁基氢锡 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 silver nitrate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 nickel dichloride 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 、 乙腈 、 苯 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 183.99h， 生成 (5E,7E,9E)-(2R,4S,11S,13S,16R)-13-Benzyloxy-17-(tert-butyl-diphenyl-silanyloxy)-11-methoxy-2,4,10,16-tetramethyl-heptadeca-5,7,9-trienal
  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：

  1,5-anhydro-3-O-benzyl-6-O-tert-butyldimetylsilyl-2-deoxy-D-arabino-hex-1-enopyranose 、 甲基磺酰氯 在 吡啶 作用下， 反应 12.0h， 以99%的产率得到Methanesulfonic acid (2R,3S,4R)-4-benzyloxy-2-(tert-butyl-dimethyl-silanyloxymethyl)-3,4-dihydro-2H-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