(3S)-5-benzyloxy-3-(tert-butyldimethylsilyl)oxypentanal | 198754-78-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3S)-5-benzyloxy-3-(tert-butyldimethylsilyl)oxypentanal
• 英文别名: (3S)-3-[tert-butyl(dimethyl)silyl]oxy-5-phenylmethoxypentanal
• CAS: 198754-78-8
• 化学式: C₁₈H₃₀O₃Si
• 分子量: 322.52
• InChiKey: DCONHETYWXPMGA-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.57
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S)-5-benzyloxy-3-(tert-butyldimethylsilyl)oxypentanal 在 2,6-二甲基吡啶 、 正丁基锂 、 potassium tert-butylate 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 51.5h， 生成 (3S,4S,6S)-8-benzyloxy-4-(triisopropylsilyl)oxy-3-methyloct-1-en-6-ol
  参考文献：
  名称：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.

  DOI：

  10.1021/jo0503862
• 作为产物：
  描述：

  3-苄氧基丙醛 在 咪唑 、 nickel boride 、 氢气 、 二异丁基氢化铝 、 (S)-4-isopropyl-1,3,2-oxazaborolidin-5-one 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 42.0h， 生成 (3S)-5-benzyloxy-3-(tert-butyldimethylsilyl)oxypentanal
  参考文献：
  名称：

  Enantioselective acyclic stereoselection under catalyst control—III. A very short asymmetric synthesis of the bryostatin C1C9 segment using the chiral oxazaborolidinone-promoted aldol reaction

  摘要：

  A very short asymmetric synthesis of the bryostatin C-1-C-9 segment was achieved by three sequential chiral oxazaborolidinone-promoted aldol reactions under 'catalyst control'. This synthetic methodology is based on a direct asymmetric incorporation of two acetate and one isobutyrate synthones into the framework. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00461-8

文献信息

• Formal Total Synthesis of (+)-Neopeltolide
  作者：Sudhakar Athe、Balla Chandrasekhar、Saumya Roy、Tapan Kumar Pradhan、Subhash Ghosh

  DOI：10.1021/jo301425c

  日期：2012.11.2

  This paper describes the formal total synthesis of (+)-neopeltolide, a cytotoxic macrolide isolated from the marine sponge Neopeltidae. The key features of the synthesis include an asymmetric Evans alkylation to fix the C9-methyl center, Jacobsen hydrolytic kinetic resolution of terminal epoxides followed by their regioselective opening to fix the stereocenters at the C11 and C13 positions, respectively

  本文描述了（+）-neopeltolide的正式全合成，neopeltolide是一种从海洋海绵Neopeltidae中分离出来的细胞毒性大环内酯。合成的关键特征包括固定C9-甲基中心的不对称伊文思烷基化，末端环氧化物的Jacobsen水解动力学拆分，以及随后的区域选择性开放，分别将Pd催化的oxa-固定在C11和C13位置的立体中心。迈克尔反应以构建四氢吡喃环，并进行山口大内酯化以形成分子的大环核心。
• Stereochemical Assignment of the C21–C38 Portion of the Desertomycin/Oasomycin Class of Natural Products by Using Universal NMR Databases: Prediction
  作者：Yoshihisa Kobayashi、Choon-Hong Tan、Yoshito Kishi

  DOI：10.1002/1521-3773(20001201)39:23<4279::aid-anie4279>3.0.co;2-r

  日期：2000.12.1

  Stereochemistry can be predicted: The stereoselective synthesis of the C21-C38 degradation product derived from oasomycins A and B has confirmed the stereochemistry predicted from a comparitive study of the NMR chemical shifts of the C21-C38 portion of the natural products with those obtained for its diastereomers.

  立体化学可以预测：来自大霉素 A 和 B 的 C21-C38 降解产物的立体选择性合成证实了从天然产物的 C21-C38 部分的 NMR 化学位移的比较研究中预测的立体化学与为其获得的那些化学位移的比较研究。非对映体。
• Intramolecular palladium catalyzed alkoxy carbonylation of 6-hydroxy-1-octenes. Stereoselective synthesis of substituted tetrahydropyrans
  作者：James D. White、Jian Hong、Lonnie A. Robarge

  DOI：10.1016/s0040-4039(98)02693-8

  日期：1999.2

  The reaction of hydroxy alkenes 5, 7, and 8 with CO and MeOH in the presence of PdCl2 and CuCl2 gave tetrahydropyrans 9, 11, and 12, respectively. Yields were dependent upon the configuration of substituents in the hydroxy alkene; in all cases, the tetrahydropyran was produced with 2,6-cis configuration. (C) 1999 Elsevier Science Ltd. All rights reserved.