methyl (2Z,4R,5S,6E)-5-[tert-butyl(dimethyl)silyl]oxy-3-methoxy-4-methyl-7-[2-[2-[(3S)-3-methyl-1,4-dioxaspiro[4.4]nonan-3-yl]-1,3-thiazol-4-yl]-1,3-thiazol-4-yl]hepta-2,6-dienoate | 1092679-03-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: methyl (2Z,4R,5S,6E)-5-[tert-butyl(dimethyl)silyl]oxy-3-methoxy-4-methyl-7-[2-[2-[(3S)-3-methyl-1,4-dioxaspiro[4.4]nonan-3-yl]-1,3-thiazol-4-yl]-1,3-thiazol-4-yl]hepta-2,6-dienoate
• CAS: 1092679-03-2
• 化学式: C₃₀H₄₄N₂O₆S₂Si
• 分子量: 620.907
• InChiKey: LGIGGKFHOUFNOM-XTSBPYOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.54
• 重原子数：
  41
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  146
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  (4R,5R)-5-(tert-butyldimethylsilyloxy)-3-methoxy-4-methyl-6-oxohex-(2Z)-enoic acid methyl ester 、 (2S)-2'-{4-benzothiazolylsulfonylmethyl-[2,4']bithiazolyl}-2-hydroxypropanol cyclopentanone acetal 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以67%的产率得到methyl (2E,4R,5S,6E)-5-[tert-butyl(dimethyl)silyl]oxy-3-methoxy-4-methyl-7-[2-[2-[(3S)-3-methyl-1,4-dioxaspiro[4.4]nonan-3-yl]-1,3-thiazol-4-yl]-1,3-thiazol-4-yl]hepta-2,6-dienoate
  参考文献：
  名称：

  Asymmetric syntheses and structure elucidation of cystothiazole A metabolites of the myxobacterium Cystobacter fuscus

  摘要：

  Convergent syntheses of (14R,15)- and (14S,15)-dihydroxycystothiazole A 4 were achieved based on a Julia-Kocienski coupling between the functionalized aldehyde (2E)-6 or (2Z)-6, corresponding to the left-side, and chiral sulfones (14R)-16 and (14S)-16, bearing a bithiazole moiety corresponding to the right-side, respectively. The absolute configuration of natural (14,15)-dihydroxycystothiazoles A 4 was determined to be (4R,5S,14S) by comparison of the physical data, including the sign of specific rotation, between synthetic (2E,4R,5S,6E,14S)-4 and natural 4. Deprotections of the silyl group and cyclopentane moiety of the coupled product (2E,4R,5S,6E,14R)-17 gave (14R,15)-dihydroxycystothiazole C 5, which was consistent with natural 5 corresponding to the minor isomer, including the sign of specific rotation. Likewise, deprotection of the silyl group and cyclopentane moiety of the coupled product (2E,4R,5S,6E,14S)-17 afforded (14S,15)-dihydroxycystothiazole C 5, which was consistent with natural 5 corresponding to the major isomer, including the sign of specific rotation. Finally, convergent synthesis of 14-hydroxycystothiazole C 3 was achieved based on the modified (one-pot) Julia olefination between the aldehyde (2Z)-6 and bithiazole sulfone 22. The absolute configurations of natural 14-hydroxycystothiazole C 3 were confirmed to be (4R) and (5S). Methylation of synthetic 3 gave cystothiazole B 2. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.08.029

文献信息

• Asymmetric syntheses and structure elucidation of cystothiazole A metabolites of the myxobacterium Cystobacter fuscus
  作者：Yuki Iwaki、Shigeo Yamamura、Hiroyuki Akita

  DOI：10.1016/j.tetasy.2008.08.029

  日期：2008.9

  Convergent syntheses of (14R,15)- and (14S,15)-dihydroxycystothiazole A 4 were achieved based on a Julia-Kocienski coupling between the functionalized aldehyde (2E)-6 or (2Z)-6, corresponding to the left-side, and chiral sulfones (14R)-16 and (14S)-16, bearing a bithiazole moiety corresponding to the right-side, respectively. The absolute configuration of natural (14,15)-dihydroxycystothiazoles A 4 was determined to be (4R,5S,14S) by comparison of the physical data, including the sign of specific rotation, between synthetic (2E,4R,5S,6E,14S)-4 and natural 4. Deprotections of the silyl group and cyclopentane moiety of the coupled product (2E,4R,5S,6E,14R)-17 gave (14R,15)-dihydroxycystothiazole C 5, which was consistent with natural 5 corresponding to the minor isomer, including the sign of specific rotation. Likewise, deprotection of the silyl group and cyclopentane moiety of the coupled product (2E,4R,5S,6E,14S)-17 afforded (14S,15)-dihydroxycystothiazole C 5, which was consistent with natural 5 corresponding to the major isomer, including the sign of specific rotation. Finally, convergent synthesis of 14-hydroxycystothiazole C 3 was achieved based on the modified (one-pot) Julia olefination between the aldehyde (2Z)-6 and bithiazole sulfone 22. The absolute configurations of natural 14-hydroxycystothiazole C 3 were confirmed to be (4R) and (5S). Methylation of synthetic 3 gave cystothiazole B 2. (C) 2008 Elsevier Ltd. All rights reserved.