2(R)-methoxy-4(S)-<(tert-butyldiphenylsilyl)oxy>-2,3-dihydro-4H-pyran | 158718-95-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2(R)-methoxy-4(S)-<(tert-butyldiphenylsilyl)oxy>-2,3-dihydro-4H-pyran
• 英文别名: tert-butyl-[[(2R,4S)-2-methoxy-3,4-dihydro-2H-pyran-4-yl]oxy]-diphenylsilane
• CAS: 158718-95-7
• 化学式: C₂₂H₂₈O₃Si
• 分子量: 368.548
• InChiKey: QQEXERIFSPRLJD-WIYYLYMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2(R)-methoxy-4(S)-<(tert-butyldiphenylsilyl)oxy>-2,3-dihydro-4H-pyran 在 盐酸 、 aluminum oxide 、 四(三苯基膦)钯 、 三丁基氯化锡 、 叔丁基锂 、 sodium cyanoborohydride 、 溶剂黄146 、 三乙胺 、 pyridinium chlorochromate 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 14.0h， 生成 (6Z,8E,10E,14Z)-(3R,5S,12R)-3,12-Bis-(tert-butyl-diphenyl-silanyloxy)-5-hydroxy-icosa-6,8,10,14-tetraenoic acid methyl ester
  参考文献：
  名称：

  3-Hydroxyleukotriene B4 (3-OH-LTB4): Total Synthesis and Stereochemical Assignment.

  摘要：

  The asymmetric total synthesis of 3-hydroxyleukotriene B-4 (3-OH-LTB(4)), an ethanol-inducible proinflammatory autacoid, was achieved using a triply convergent strategy for the sequential union of propargylic arsonium salt 3 with pyranosides 2a,b and furanose 4. Both saccharide subunits were derived from commercial 2-deoxy-D-ribose. The key transformation involved palladium-mediated coupling of bromoacetylenide 9 with stannylglycal 6a,b. Subsequent Rieke zinc hydrogenation of acetylene 10a,b and controlled ionic reduction of the cross-conjugated cyclic enol ether using NaBH3CN at pH similar to 4-4.5 established the cis-Delta(6,7)-olefin and C(5)-hydroxyl stereochemistry, respectively, and led to 11a,b. Methyllactol hydrolysis, PCC oxidation, methanolysis, and desilylation afforded 3(R)- and 3(S)-OH-LTB(4) methyl esters, respectively. On the basis of chromatographic and mass spectral comparisons, enzymatically derived 3-OH-LTB(4) is composed principally of the 3(S)-isomer (>95%).

  DOI：

  10.1021/ja00091a004
• 作为产物：
  描述：

  methyl 2-deoxy-β-D-erythro-pentopyranoside 在 吡啶 、 silver nitrate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 2(R)-methoxy-4(S)-<(tert-butyldiphenylsilyl)oxy>-2,3-dihydro-4H-pyran
  参考文献：
  名称：

  3-Hydroxyleukotriene B4 (3-OH-LTB4): Total Synthesis and Stereochemical Assignment.

  摘要：

  The asymmetric total synthesis of 3-hydroxyleukotriene B-4 (3-OH-LTB(4)), an ethanol-inducible proinflammatory autacoid, was achieved using a triply convergent strategy for the sequential union of propargylic arsonium salt 3 with pyranosides 2a,b and furanose 4. Both saccharide subunits were derived from commercial 2-deoxy-D-ribose. The key transformation involved palladium-mediated coupling of bromoacetylenide 9 with stannylglycal 6a,b. Subsequent Rieke zinc hydrogenation of acetylene 10a,b and controlled ionic reduction of the cross-conjugated cyclic enol ether using NaBH3CN at pH similar to 4-4.5 established the cis-Delta(6,7)-olefin and C(5)-hydroxyl stereochemistry, respectively, and led to 11a,b. Methyllactol hydrolysis, PCC oxidation, methanolysis, and desilylation afforded 3(R)- and 3(S)-OH-LTB(4) methyl esters, respectively. On the basis of chromatographic and mass spectral comparisons, enzymatically derived 3-OH-LTB(4) is composed principally of the 3(S)-isomer (>95%).

  DOI：

  10.1021/ja00091a004

文献信息

• Total synthesis of the ethanol inducible, proinflammatory autacoid 3(S)-hydroxy-leukotriene B4 (3-OH-LTB4) and analogues
  作者：Kamlesh Chauhan、Rama K. Bhatt、J.R. Falck、Jorge H. Capdevila

  DOI：10.1016/s0040-4039(00)73170-4

  日期：1994.3

  3(S)-Hydroxy-Leukotriene B-4 (1a), its 3(R)-epimer 1b, and a 14,15-acetylenic analogue were efficiently prepared via chelation-controlled reduction of ketone 12, obtained by acetylide addition to chiral beta-hydroxylactones 7/9.
• 3-Hydroxyleukotriene B4 (3-OH-LTB4): Total Synthesis and Stereochemical Assignment.
  作者：Rama K. Bhatt、Kamlesh Chauhan、Pat Wheelan、J. R. Falck、Robert C. Murphy

  DOI：10.1021/ja00091a004

  日期：1994.6

  The asymmetric total synthesis of 3-hydroxyleukotriene B-4 (3-OH-LTB(4)), an ethanol-inducible proinflammatory autacoid, was achieved using a triply convergent strategy for the sequential union of propargylic arsonium salt 3 with pyranosides 2a,b and furanose 4. Both saccharide subunits were derived from commercial 2-deoxy-D-ribose. The key transformation involved palladium-mediated coupling of bromoacetylenide 9 with stannylglycal 6a,b. Subsequent Rieke zinc hydrogenation of acetylene 10a,b and controlled ionic reduction of the cross-conjugated cyclic enol ether using NaBH3CN at pH similar to 4-4.5 established the cis-Delta(6,7)-olefin and C(5)-hydroxyl stereochemistry, respectively, and led to 11a,b. Methyllactol hydrolysis, PCC oxidation, methanolysis, and desilylation afforded 3(R)- and 3(S)-OH-LTB(4) methyl esters, respectively. On the basis of chromatographic and mass spectral comparisons, enzymatically derived 3-OH-LTB(4) is composed principally of the 3(S)-isomer (>95%).