(4R,5R)-5-(tert-butyldimethylsilyloxy)-3-methoxy-4-methyl-6-oxohex-(2Z)-enoic acid methyl ester | 1092678-85-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4R,5R)-5-(tert-butyldimethylsilyloxy)-3-methoxy-4-methyl-6-oxohex-(2Z)-enoic acid methyl ester
• 英文别名: methyl (Z,4R,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-methoxy-4-methyl-6-oxohex-2-enoate
• CAS: 1092678-85-7
• 化学式: C₁₅H₂₈O₅Si
• 分子量: 316.47
• InChiKey: GXQCHBDCBSJHLE-ZSCUQQAQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4R,5R)-5-(tert-butyldimethylsilyloxy)-3-methoxy-4-methyl-6-oxohex-(2Z)-enoic acid methyl ester 、 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 生成 、
  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
• 作为产物：
  描述：

  (4R,5R)-5-(tert-butyldimethylsilyloxy)-6-hydroxy-3-methoxy-4-methylhex-(2Z)-enoic acid metyl ester 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 以92%的产率得到(4R,5R)-5-(tert-butyldimethylsilyloxy)-3-methoxy-4-methyl-6-oxohex-(2Z)-enoic acid methyl ester
  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.