isobutyl 5-(benzyloxy)-3-oxopentanoate | 106064-33-9

• 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: isobutyl 5-(benzyloxy)-3-oxopentanoate
• 英文别名: isobutyl 5-benzyloxy-3-oxopentanoate；Pentanoic acid, 3-oxo-5-(phenylmethoxy)-, 2-methylpropyl ester；2-methylpropyl 3-oxo-5-phenylmethoxypentanoate
• CAS: 106064-33-9
• 化学式: C₁₆H₂₂O₄
• 分子量: 278.348
• InChiKey: SNBIKQIVDAOHBV-UHFFFAOYSA-N

物化性质

• 沸点：
  374.7±22.0 °C(Predicted)
• 密度：
  1.063±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  isobutyl 5-(benzyloxy)-3-oxopentanoate 在 2,6-二甲基吡啶 、 Ru₂Cl₄((S)-BINAP)2 、 氢气 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 三乙胺 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 甲苯 为溶剂， -78.0~55.0 ℃ 、5.0 MPa 条件下， 生成 (3S,5S,6R)-6-methyl-1-phenylmethoxy-5-tri(propan-2-yl)silyloxyoct-7-en-3-ol
  参考文献：
  名称：

  Intramolecular palladium catalyzed alkoxy carbonylation of 6-hydroxy-1-octenes. Stereoselective synthesis of substituted tetrahydropyrans

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(98)02693-8
• 作为产物：
  描述：

  苄基氯甲基醚 、 乙酰乙酸异丁酯 在 sodium hydride 、 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到isobutyl 5-(benzyloxy)-3-oxopentanoate
  参考文献：
  名称：

  Synthetic Studies of Complex Immunostimulants from Quillaja saponaria:  Synthesis of the Potent Clinical Immunoadjuvant QS-21A_api

  摘要：

  QS-21 is one of the most promising new adjuvants for immune response potentiation and dose-sparing in vaccine therapy given its exceedingly high level of potency and its favorable toxicity profile. Melanoma, breast cancer, small cell lung cancer, prostate cancer, HIV-1, and malaria are among the numerous maladies targeted in more than 80 recent and ongoing vaccine therapy clinical trials involving QS-21 as a critical adjuvant component for immune response augmentation. QS-21 is a natural product immunostimulatory adjuvant, eliciting both T-cell- and antibody-mediated immune responses with microgram doses. Herein is reported the synthesis of QS-21A(api) in a highly modular strategy, applying novel glycosylation methodologies to a convergent construction of the potent saponin immunostimulant. The chemical synthesis of QS-21 offers unique opportunities to probe its mode of biological action through the preparation of otherwise unattainable nonnatural saponin analogues.

  DOI：

  10.1021/ja062364i

文献信息

• Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga <i>Polycavernosa </i><i>t</i><i>sudai</i>
  作者：Paul R. Blakemore、Cindy C. Browder、Jian Hong、Christopher M. Lincoln、Pavel A. Nagornyy、Lonnie A. Robarge、Duncan J. Wardrop、James D. White

  DOI：10.1021/jo0503862

  日期：2005.7.1

  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%.
• Substrate modification as a means of enhancing the enantioselectivity of microbial reductions of .beta.-keto esters. A (R)- or (S)-1,3,5-trihydroxypentane synthon
  作者：Dee W. Brooks、Rosemary P. Kellogg、Curt S. Cooper

  DOI：10.1021/jo00378a007

  日期：1987.1
• BROOKS D. W.; KELLOGG R. P.; COOPER C. S., J. ORG. CHEM., 52,(1987) N 2, 192-196
  作者：BROOKS D. W.、 KELLOGG R. P.、 COOPER C. S.

  DOI：——

  日期：——
• 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.
• Synthetic Studies of Complex Immunostimulants from <i>Quillaja saponaria</i>:  Synthesis of the Potent Clinical Immunoadjuvant QS-21A_a_pi
  作者：Yong-Jae Kim、Pengfei Wang、Mauricio Navarro-Villalobos、Bridget D. Rohde、DerryBerry、David Y. Gin

  DOI：10.1021/ja062364i

  日期：2006.9.1

  QS-21 is one of the most promising new adjuvants for immune response potentiation and dose-sparing in vaccine therapy given its exceedingly high level of potency and its favorable toxicity profile. Melanoma, breast cancer, small cell lung cancer, prostate cancer, HIV-1, and malaria are among the numerous maladies targeted in more than 80 recent and ongoing vaccine therapy clinical trials involving QS-21 as a critical adjuvant component for immune response augmentation. QS-21 is a natural product immunostimulatory adjuvant, eliciting both T-cell- and antibody-mediated immune responses with microgram doses. Herein is reported the synthesis of QS-21A(api) in a highly modular strategy, applying novel glycosylation methodologies to a convergent construction of the potent saponin immunostimulant. The chemical synthesis of QS-21 offers unique opportunities to probe its mode of biological action through the preparation of otherwise unattainable nonnatural saponin analogues.