(2S,4S,5S,6E)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-6-octen-3-one | 116546-79-3

• 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,4S,5S,6E)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-6-octen-3-one
• 英文别名: (E,2S,4S,5S)-5-hydroxy-2,4-dimethyl-1-phenylmethoxyoct-6-en-3-one
• CAS: 116546-79-3；116661-38-2；128241-46-3；141611-63-4
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: QBQCAHLOYCXKFV-SNXFNUAHSA-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

• 作为反应物：
  描述：

  (2S,4S,5S,6E)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-6-octen-3-one 在 palladium on activated charcoal 、 镍 盐酸 、 4-二甲氨基吡啶 、 sodium periodate 、 sodium dihydrogenphosphate 、 四氧化锇 、 2-甲基-2-丁烯 、 草酰氯 、 LiDBB 、 pH 7 buffer 、 lithium diethylamide 、 sodium perchlorate 、 氢气 、 4-甲基苯磺酸吡啶 、 potassium hydride 、 双(三甲基硅烷基)氨基钾 、 镍 、 对甲苯磺酸 、 溶剂黄146 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 三乙胺 、 tetramethylammonium triacetoxyborohydride 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 甲苯 、 乙腈 、 叔丁醇 为溶剂， 反应 173.25h， 生成 (2R,3S,4R,5S,6S,9R,10R,11R,12R,13R)-9,11-dihydroxy-3,5-(isopropylidenedioxy)-2,4,6,10,12,13-hexamethyl-8-methylenetetradecanolide
  参考文献：
  名称：

  Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one

  摘要：

  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).

  DOI：

  10.1021/ja00104a010
• 作为产物：
  描述：

  2,2,2-三氯乙酰胺苄酯 在 三氟甲磺酸 、 pH 7 buffer 、 氯代二环己基硼烷 、 双氧水 、 三甲基铝 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 环己烷 为溶剂， 反应 19.25h， 生成 (2S,4S,5S,6E)-1-(benzyloxy)-5-hydroxy-2,4-dimethyl-6-octen-3-one
  参考文献：
  名称：

  Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one

  摘要：

  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).

  DOI：

  10.1021/ja00104a010

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％。
• Substrate-Controlled Aldol Reactions of Chiral Ethyl Ketones: Application to the Total Synthesis of Oleandomycin
  作者：Ian Paterson、Richard A. Ward、Pedro Romea、Roger D. Norcross

  DOI：10.1021/ja00087a068

  日期：1994.4