(2S,4R,5R)-2-benzoyloxy-5-hydroxy-4,6-dimethylheptan-3-one | 161985-39-3

• 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: (2S,4R,5R)-2-benzoyloxy-5-hydroxy-4,6-dimethylheptan-3-one
• 英文别名: [(2S,4R,5R)-5-hydroxy-4,6-dimethyl-3-oxoheptan-2-yl] benzoate
• CAS: 161985-39-3
• 化学式: C₁₆H₂₂O₄
• 分子量: 278.348
• InChiKey: LALRBBUKZWBZIB-MBNYWOFBSA-N

物化性质

• 沸点：
  415.2±25.0 °C(Predicted)
• 密度：
  1.089±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,4R,5R)-2-benzoyloxy-5-hydroxy-4,6-dimethylheptan-3-one 在 Wilkinson's catalyst 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 四氧化锇 、 N-甲基吲哚酮 、 三氟甲磺酸二丁硼 、 四丁基氟化铵 、 氢气 、 4-甲基苯磺酸吡啶 、 四氯化钛 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 苯 为溶剂， -94.0~20.0 ℃ 、1.5 MPa 条件下， 反应 48.84h， 生成 (3S,4R,5S,6R,7S)-8-Benzyloxy-6-(tert-butyl-dimethyl-silanyloxy)-4-hydroxy-1-((4R,5S,6R)-6-isopropyl-2,2,5-trimethyl-[1,3]dioxan-4-yl)-7-methoxy-3,5-dimethyl-octan-2-one
  参考文献：
  名称：

  Stereocontrolled aldol additions to α-methylene-β-alkoxy aldehydes: Application to the synthesis of a C13C25 segment of bafilomycin A1

  摘要：

  A boron-mediated, syn-aldol coupling between ethyl ketone 8 and aldehyde 9, followed by directed hydrogenation at C-16 and acetonide hydrolysis, gives the C-13-C-25 segment 6 of bafilomycin A(1).

  DOI：

  10.1016/0040-4039(94)02205-p
• 作为产物：
  描述：

  (S)-2-hydroxy-3-pentanone 在 4-二甲氨基吡啶 、 二甲基十二/十四烷基叔胺 、 氯代二环己基硼烷 、 双氧水 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 32.0h， 生成 (2S,4R,5R)-2-benzoyloxy-5-hydroxy-4,6-dimethylheptan-3-one
  参考文献：
  名称：

  Studies in polypropionate synthesis: High π-face selectivity in syn and anti aldol reactions of chiral boron enolates of lactate-derived ketones

  摘要：

  Use of (c)Hex(2)BCl/Me(2)NEt in the aldol reactions of the alpha'-benzoyloxy ketone 7 with aldehydes leads to high stereoselectivity (97-99.5% ds) for the crystalline anti adducts 11. Under similar conditions, the corresponding benzyl ether 6 favours formation of the syn adducts 9.

  DOI：

  10.1016/0040-4039(94)88434-x

文献信息

• Manipulation of the aldol adducts from lactate-derived ketones. A versatile chiral auxiliary for the asymmetric synthesis of β-hydroxy carbonyl compounds
  作者：Ian Paterson、Debra J. Wallace

  DOI：10.1016/0040-4039(94)88435-8

  日期：1994.11

  The ketones 1 and 2 can be transformed into a wide range of enantiomerically-pure anti and syn α-methyl-β-hydroxy ketones and aldehydes. The α′-methyl group in 5 and 11 may be retained, demonstrating the use of the lactate-derived group as an optional chiral auxiliary.

  酮1和2可以转化到广泛范围的对映体纯的抗和顺式α甲基β羟基酮和醛。可以保留5和11中的α'-甲基，这表明使用乳酸酯衍生的基团作为任选的手性助剂。
• Polyketide Synthesis Using the Boron-Mediated, anti-Aldol Reactions of Lactate-Derived Ketones: Total Synthesis of (-)-ACRL Toxin IIIB
  作者：Ian Paterson

  DOI：10.1055/s-1998-5929

  日期：1998.3

  The boron-mediated, anti-selective, aldol reactions of ketone 2 (and related derivatives) proceed with high levels of asymmetric induction, diastereoselectivities of up to 200:1 in favour of the aldol adducts 4 are obtained with achiral aldehydes and reagent control operates with chiral aldehydes. These lactate-derived ketones provide a versatile chiral auxiliary for the synthesis of beta-hydroxy carbonyl compounds. Oxidative removal of the auxiliary provides enantiomerically pure aldehydes 5, while reductive deoxygenation gives the corresponding ethyl ketones 6. This practical asymmetric methodology for generating anti-aldols is illustrated by an efficient total synthesis of (-)-ACRL toxin IIIB (7), which proceeds in 15 steps from 2 with 21% overall yield and 88% diastereoselectivity.
• A Retro-Claisen Approach to Dolabriferol
  作者：Troy Lister、Michael V. Perkins

  DOI：10.1021/ol060347s

  日期：2006.4.1

  The protected precursor 30 to dolabriferol was generated by a DBU-induced, ester-forming, retro-Claisen process. The required linear carbon chain present in 22 was synthesized by a stereoselective lithium aldol reaction. The necessary aldehyde and ketone fragments were synthesized using stereocontrolled aldol reactions with the ethyl (S)-lactate derived ketone 13.
• Stereocontrolled aldol additions to α-methylene-β-alkoxy aldehydes: Application to the synthesis of a C13C25 segment of bafilomycin A1
  作者：Ian Paterson、Shelley Bower、Malcolm D. McLeod

  DOI：10.1016/0040-4039(94)02205-p

  日期：1995.1

  A boron-mediated, syn-aldol coupling between ethyl ketone 8 and aldehyde 9, followed by directed hydrogenation at C-16 and acetonide hydrolysis, gives the C-13-C-25 segment 6 of bafilomycin A(1).
• Studies in polypropionate synthesis: High π-face selectivity in syn and anti aldol reactions of chiral boron enolates of lactate-derived ketones
  作者：Ian Paterson、Debra J. Wallace、Silvia M. Velázquez

  DOI：10.1016/0040-4039(94)88434-x

  日期：1994.11

  Use of (c)Hex(2)BCl/Me(2)NEt in the aldol reactions of the alpha'-benzoyloxy ketone 7 with aldehydes leads to high stereoselectivity (97-99.5% ds) for the crystalline anti adducts 11. Under similar conditions, the corresponding benzyl ether 6 favours formation of the syn adducts 9.