(4R,5R)-5-(tert-butyldimethylsilyloxy)-3-methoxy-4-methyl-6-oxohex-(2E)-enoic acid methyl ester | 1006629-79-3

• 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-(2E)-enoic acid methyl ester
• 英文别名: methyl (E,4R,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-methoxy-4-methyl-6-oxohex-2-enoate
• CAS: 1006629-79-3
• 化学式: C₁₅H₂₈O₅Si
• 分子量: 316.47
• InChiKey: GXQCHBDCBSJHLE-XLCKQVHISA-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-(2E)-enoic acid methyl ester 、 (2R)-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76%的产率得到
  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-(2E)-enoic acid methyl ester 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以92%的产率得到(4R,5R)-5-(tert-butyldimethylsilyloxy)-3-methoxy-4-methyl-6-oxohex-(2E)-enoic acid methyl ester
  参考文献：
  名称：

  Concise Syntheses of Cystothiazoles A, C, D, and Melithiazol B

  摘要：

  通过茱莉亚偶联，最终分子左半部分的官能化醛 5b 与右半部分的芳基砜 6 或 7（含有双噻唑分子）实现了环噻唑 C 1 和 D 3 的聚合合成。将 1 和 3 甲基化后，分别得到胱噻唑 A 2 和三甲基噻唑 B 4。与之前报道的官能化醛 5a（从 10 开始，分 7 步制备；13%）相比，通过本方法制备 5b 的总收率（从 (2R,3S)-3-甲基戊-4-炔-1,2-二醇 10 开始，分 5 步制备；57%）有所提高。通过应用改进的 Julia 偶联法，与 Wittig 法（6E/6Z=4 : 1-6.9 : 1）相比，提高了偶联产物（15 或 19）的 (6E) 形式对相应 (6Z) 形式的选择性（6E/6Z=20 : 1-26 : 1）。

  DOI：

  10.1248/cpb.55.1610

文献信息

• Concise Syntheses of Cystothiazoles A, C, D, and Melithiazol B
  作者：Yuki Iwaki、Hiroyuki Akita

  DOI：10.1248/cpb.55.1610

  日期：——

  A convergent synthesis of cystothiazoles C 1 and D 3 was achieved based on Julia coupling between the functionalized aldehyde 5b, corresponding to left half of the final molecule, and aryl sulfone 6 or 7, bearing a bithiazole moiety, corresponding to right half. Methylation of 1 and 3 gave cystothiazole A 2 and melithiazol B 4, respectively. The overall yield (5 steps from (2R,3S)-3-methylpent-4-yne-1,2-diol 10; 57%) of 5b via the present route was improved in comparison to that of the previously reported functionalized aldehyde 5a (7 steps from 10; 13%). By applying the modified Julia coupling method, selectivity (6E/6Z=20 : 1—26 : 1) toward the (6E)-form of the coupled products (15 or 19) against the corresponding (6Z)-form was improved in comparison to the Wittig method (6E/6Z=4 : 1—6.9 : 1).

  通过茱莉亚偶联，最终分子左半部分的官能化醛 5b 与右半部分的芳基砜 6 或 7（含有双噻唑分子）实现了环噻唑 C 1 和 D 3 的聚合合成。将 1 和 3 甲基化后，分别得到胱噻唑 A 2 和三甲基噻唑 B 4。与之前报道的官能化醛 5a（从 10 开始，分 7 步制备；13%）相比，通过本方法制备 5b 的总收率（从 (2R,3S)-3-甲基戊-4-炔-1,2-二醇 10 开始，分 5 步制备；57%）有所提高。通过应用改进的 Julia 偶联法，与 Wittig 法（6E/6Z=4 : 1-6.9 : 1）相比，提高了偶联产物（15 或 19）的 (6E) 形式对相应 (6Z) 形式的选择性（6E/6Z=20 : 1-26 : 1）。
• 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.