tritert-butyl (1S,3S,4S,5R,6R,7R)-6-[(E,4S,6S)-4,6-dimethyloct-2-enoyl]oxy-4-hydroxy-1-[(4S,5R)-4-[(4-methoxyphenyl)methoxymethoxy]-5-methyl-3-oxo-6-phenylhexyl]-7-triethylsilyloxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylate | 185201-22-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tritert-butyl (1S,3S,4S,5R,6R,7R)-6-[(E,4S,6S)-4,6-dimethyloct-2-enoyl]oxy-4-hydroxy-1-[(4S,5R)-4-[(4-methoxyphenyl)methoxymethoxy]-5-methyl-3-oxo-6-phenylhexyl]-7-triethylsilyloxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylate
• CAS: 185201-22-3
• 化学式: C₅₉H₉₀O₁₆Si
• 分子量: 1083.44
• InChiKey: ROXVAWGRXZKMKF-JZCWYPEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.33
• 重原子数：
  76
• 可旋转键数：
  34
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  198
• 氢给体数：
  1
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  tritert-butyl (1S,3S,4S,5R,6R,7R)-6-[(E,4S,6S)-4,6-dimethyloct-2-enoyl]oxy-4-hydroxy-1-[(4S,5R)-4-[(4-methoxyphenyl)methoxymethoxy]-5-methyl-3-oxo-6-phenylhexyl]-7-triethylsilyloxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylate 在 lead(IV) acetate 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride 、 二甲基硫 、 乙基溴化镁 、 盐酸羟胺 、 水 、 sodium acetate 、 氟化氢吡啶 、 臭氧 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 17.38h， 生成 (1S-(1α,3α,4β,5α,6α,7β))-1-(3-oxopropyl)-4,6,7-trihydroxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylic acid 3,4,5-tris(1,1-dimethylethyl) ester
  参考文献：
  名称：

  Total Synthesis of Zaragozic Acid A (Squalestatin S1). Degradation to a Relay Compound and Reassembly of the Natural Product

  摘要：

  Zaragozic acid A (squalestatin S1) (1) was converted into the simpler derivative 2, which was reconverted into the natural product, thus establishing 2 as a viable relay compound for total synthesis of 1. The degradation (Scheme 1) consisted of formation of the tri-tert-butyl ester (3), from which the two side chains were sequentially removed to obtain 8. Aldehyde 8 was converted into dimethyl acetal 2 in standard fashion. The C6 acyl side chain 14 was prepared from (S)-2-methylbutanol (''active amyl alcohol''), and the desired 4S configuration was obtained by use of Evans asymmetric enolate methylation (Scheme 2). The C1 alkyl side chain was prepared as stannane 23a from (R)-2-methyl-3-phenylpropanol (21) as shown in Scheme 5. For conversion of 2 back into zaragozic acid A, the dimethyl acetal was first converted into the cyclic acetal 17, thus protecting the C7 hydroxyl group. The remaining hydroxyl group was then acylated with acid 14 to obtain 18, which was transformed into aldehyde 20 (Scheme 4). The C1 alkyl chain was elaborated by the addition of a chiral alpha-alkoxyorganocerium reagent, obtained from 23a, to aldehyde 20. The resulting mixture of diastereomeric secondary alcohols was converted into zaragozic acid A (1) in six steps (Scheme 6).

  DOI：

  10.1021/jo961533m
• 作为产物：
  描述：

  tritert-butyl (1S,3S,4S,5R,6R,7R)-6-[(E,4S,6S)-4,6-dimethyloct-2-enoyl]oxy-4-hydroxy-1-[(4S,5R)-3-hydroxy-4-[(4-methoxyphenyl)methoxymethoxy]-5-methyl-6-phenylhexyl]-7-triethylsilyloxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylate 在 吡啶 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.67h， 以92%的产率得到tritert-butyl (1S,3S,4S,5R,6R,7R)-6-[(E,4S,6S)-4,6-dimethyloct-2-enoyl]oxy-4-hydroxy-1-[(4S,5R)-4-[(4-methoxyphenyl)methoxymethoxy]-5-methyl-3-oxo-6-phenylhexyl]-7-triethylsilyloxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylate
  参考文献：
  名称：

  Total Synthesis of Zaragozic Acid A (Squalestatin S1). Degradation to a Relay Compound and Reassembly of the Natural Product

  摘要：

  Zaragozic acid A (squalestatin S1) (1) was converted into the simpler derivative 2, which was reconverted into the natural product, thus establishing 2 as a viable relay compound for total synthesis of 1. The degradation (Scheme 1) consisted of formation of the tri-tert-butyl ester (3), from which the two side chains were sequentially removed to obtain 8. Aldehyde 8 was converted into dimethyl acetal 2 in standard fashion. The C6 acyl side chain 14 was prepared from (S)-2-methylbutanol (''active amyl alcohol''), and the desired 4S configuration was obtained by use of Evans asymmetric enolate methylation (Scheme 2). The C1 alkyl side chain was prepared as stannane 23a from (R)-2-methyl-3-phenylpropanol (21) as shown in Scheme 5. For conversion of 2 back into zaragozic acid A, the dimethyl acetal was first converted into the cyclic acetal 17, thus protecting the C7 hydroxyl group. The remaining hydroxyl group was then acylated with acid 14 to obtain 18, which was transformed into aldehyde 20 (Scheme 4). The C1 alkyl chain was elaborated by the addition of a chiral alpha-alkoxyorganocerium reagent, obtained from 23a, to aldehyde 20. The resulting mixture of diastereomeric secondary alcohols was converted into zaragozic acid A (1) in six steps (Scheme 6).

  DOI：

  10.1021/jo961533m

文献信息

• Total Synthesis of Zaragozic Acid A (Squalestatin S1). Degradation to a Relay Compound and Reassembly of the Natural Product
  作者：Doris Stoermer、Stéphane Caron、Clayton H. Heathcock

  DOI：10.1021/jo961533m

  日期：1996.1.1

  Zaragozic acid A (squalestatin S1) (1) was converted into the simpler derivative 2, which was reconverted into the natural product, thus establishing 2 as a viable relay compound for total synthesis of 1. The degradation (Scheme 1) consisted of formation of the tri-tert-butyl ester (3), from which the two side chains were sequentially removed to obtain 8. Aldehyde 8 was converted into dimethyl acetal 2 in standard fashion. The C6 acyl side chain 14 was prepared from (S)-2-methylbutanol (''active amyl alcohol''), and the desired 4S configuration was obtained by use of Evans asymmetric enolate methylation (Scheme 2). The C1 alkyl side chain was prepared as stannane 23a from (R)-2-methyl-3-phenylpropanol (21) as shown in Scheme 5. For conversion of 2 back into zaragozic acid A, the dimethyl acetal was first converted into the cyclic acetal 17, thus protecting the C7 hydroxyl group. The remaining hydroxyl group was then acylated with acid 14 to obtain 18, which was transformed into aldehyde 20 (Scheme 4). The C1 alkyl chain was elaborated by the addition of a chiral alpha-alkoxyorganocerium reagent, obtained from 23a, to aldehyde 20. The resulting mixture of diastereomeric secondary alcohols was converted into zaragozic acid A (1) in six steps (Scheme 6).