(2S,4R,5S,6E)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-6-octen-3-one | 160796-66-7

• 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,5S,6E)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-6-octen-3-one
• 英文别名: (2S,4R,5S,6E)-1-benzyloxy-5-hydroxy-2,4-dimethyl-6-octen-3-one；(E,2S,4R,5S)-5-hydroxy-2,4-dimethyl-1-phenylmethoxyoct-6-en-3-one
• CAS: 160796-66-7
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: QBQCAHLOYCXKFV-DDCPPBFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,2,2-三氯乙酰胺苄酯 在 三氟甲磺酸 Me2AlN(Me)OMe 、 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (2S,4R,5S,6E)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-6-octen-3-one
  参考文献：
  名称：

  手性乙基酮的醛醇缩合：通过手性硼试剂控制。

  摘要：

  在Et 3 N存在下，手性试剂（+）-和（-）-Ipc）2 BOTf用于控制手性乙酮5与前手性醛的醛醇缩合反应。的SS异构体，6或8，或SA异构体，7或9，然后形成在> 99％ee的并用高达93％的非对映选择性。

  DOI：

  10.1016/s0040-4039(00)80157-4

文献信息

• Aldol reactions in polypropionate synthesis: High π-face selectivity of enol borinates from α-chiral methyl and ethyl ketones under substrate control
  作者：Ian Paterson、Jonathan M. Goodman、Masahiko Isaka

  DOI：10.1016/s0040-4039(01)93440-9

  日期：——

  Use of (c-C6H11)2BCl in the anti-selective aldol reaction of the α-chiral ethylketone 2 leads to high stereoselectivity (>94%) for the 1,2-anti-2,4-anti isomer 7. The related α-chiral methylketone aldol reaction, 8 → 9, proceeds with 84–93% diasteroselectivity for a range of boron reagents.

  在α-手性乙酮2的抗选择性羟醛反应中使用（c -C 6 H 11）2 BCl会导致1,2-抗-2,4-抗异构体7具有较高的立体选择性（> 94％）。相关的α-手性甲基酮醛醇缩醛反应8 → 9，对一系列硼试剂的非对映选择性为84–93％。
• Highly Stereoselective Aldol Reaction Based on Titanium Enolates from (<i>S</i>)-1-Benzyloxy-2-methyl-3-pentanone
  作者：Joan G. Solsona、Joaquim Nebot、Pedro Romea、Fèlix Urpí

  DOI：10.1021/jo050792l

  日期：2005.8.1

  Alternative titanium-mediated aldol procedures based on several protected β-hydroxy ethyl ketones have been surveyed. Eventually, enolization of (S)-1-benzyloxy-2-methyl-3-pentanone (1) with (i-PrO)TiCl3/i-Pr2NEt provided a very reactive enolate that afforded the corresponding 2,4-syn-4,5-syn aldol adducts in high yields and diastereomeric ratios with a broad range of aldehydes

  已经研究了基于几种受保护的β-羟乙基酮的钛介导的羟醛替代方法。最终，用（i -PrO）TiCl 3 / i -Pr 2 NEt对（S）-1-苄氧基-2-甲基-3-戊酮（1）进行烯化反应，提供了一个非常活泼的烯醇化物，提供了相应的2,4-顺-4,5-顺式羟醛加合物，具有高收率和非对映异构体比例，且具有广泛的醛类
• Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one
  作者：Ian Paterson、Roger D. Norcross、Richard A. Ward、Pedro Romea、M. Anne Lister

  DOI：10.1021/ja00104a010

  日期：1994.12

  A highly stereocontrolled total synthesis of oleandolide (2), the aglycon of the macrolide antibiotic oleandomycin (1), has been completed in 8% overall yield (20 steps longest Linear sequence, 26 steps in total) with 90% overall diastereoselectivity. Initially, reagent-controlled syn aldol reactions of (S)-1-(benzyloxy)-2-methylpentan-3-one ((S)-8) were employed to prepare adducts 6 (SS) and 7 (SA), which were elaborated to provide the two advanced fragments 33 and 27, respectively. Coupling of these fragments followed by functional group manipulation and macrolactonization gave the macrocyclic ketone 42, possessing S configuration at C-9. Elaboration of 42 to oleandolide, however, proved troublesome. Substrate-controlled syn and anti aldol reactions of ketone (S)-8, meanwhile, provided the adducts 6 (SS) and 7 (AA), which enabled synthesis, via fragments 64 and 60, of the key macrocyclic ketone intermediate 69, having R configuration at C-9. Stereoselective epoxidation of ketone 69, by reaction with dimethylsulfonium methylide under macrocyclic stereocontrol, provided the (8R)-epoxide 83; subsequent elaboration then gave oleandolide (2).
• PATERSON, IAN;LISTER, M. ANNE, TETRAHEDRON LETT., 29,(1988) N 5, 585-588
  作者：PATERSON, IAN、LISTER, M. ANNE

  DOI：——

  日期：——