(2S,4R,5R)-1-(benzyloxy)-5-hydroxy-2,4,6-trimethylhept-6-en-3-one | 116661-41-7

• 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,5R)-1-(benzyloxy)-5-hydroxy-2,4,6-trimethylhept-6-en-3-one
• 英文别名: (2S,4R,5R)-1-benzyloxy-5-hydroxy-2,4,6-trimethyl-6-hepten-3-one；(2S,4R,5R)-5-hydroxy-2,4,6-trimethyl-1-phenylmethoxyhept-6-en-3-one
• CAS: 116661-41-7
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: SCOGKZUDPUACQG-LZWOXQAQSA-N

物化性质

• 沸点：
  406.9±35.0 °C(Predicted)
• 密度：
  1.031±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 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,4R,5R)-1-(benzyloxy)-5-hydroxy-2,4,6-trimethylhept-6-en-3-one 在 palladium on activated charcoal 、 镍 盐酸 、 4-二甲氨基吡啶 、 sodium periodate 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 草酰氯 、 B-hydroxydiisopinocampheylborane 、 lithium diethylamide 、 sodium perchlorate 、 氢气 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 镍 、 二甲基亚砜 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 80.5h， 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：

  (2S)-3-(benzyloxy)-2-methylpropanal 生成 (2S,4R,5R)-1-(benzyloxy)-5-hydroxy-2,4,6-trimethylhept-6-en-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

• Formal Total Synthesis of Spirangien A
  作者：Claire Gregg、Christian Gunawan、Audrey Wai Yi Ng、Samantha Wimala、Sonali Wickremasinghe、Mark A. Rizzacasa

  DOI：10.1021/ol3033253

  日期：2013.2.1

  A formal total synthesis of the spiroketal containing cytotoxic myxobacteria metabolite spirangien A (1) is described. The approach utilizes a late introduction of the C20 alcohol that mirrors the biosynthesis of this compound. The key steps involved a high yielding cross metathesis reaction between enone 6 and alkene 7 to give E-enone 4 and a Mn-catalyzed conjugate reduction α-oxidation reaction to

  描述了含有细胞毒性粘细菌代谢产物spirangien A（1）的spiroketal的正式全合成。该方法利用了C20醇的后期引入，这反映了该化合物的生物合成。关键步骤涉及烯酮6与烯烃7之间的高产率交叉复分解反应，得到E-烯酮4，以及Mn催化的共轭还原α-氧化反应，引入C20羟基。对α-羟基酮4进行酸处理后，将螺环酮19转化为已知的螺环素A（1）高级中间螺环酮3。
• Total asymmetric synthesis of seco-acids of 9,12-anhydroerythronolide aglycons
  作者：Simon W. Ainge、Pierre Vogel

  DOI：10.1016/s0040-4039(98)00691-1

  日期：1998.6

  sulfoxides (6), the condensation of which with (3R,4S,5R,6S)-7-benzyloxy-3,5-isopropylidenedioxy-4,6-dimethylheptan-2-one (7) led to the partially-protected seco-acid of the 9,12-anhydroerythronolide aglycon (5).

  2,4-二甲基呋喃的Diels-Alder加成物与1-氰基乙烯基（1 'S）-樟脑酸酯转化为（2 R，3 R，4 S，5 S，6 R，7 R）-3,6-环氧-4,5-异丙基二烯二氧基-2,4,6-三甲基-7-[（叔丁基）-二薄荷基甲硅烷氧基]壬-1-基苯基亚砜（6），其缩合与（3 R，4 S，5 [R，6小号）-7-苄氧基-3,5-异亚丙基二4,6-二甲基庚-2-酮（7引导到部分保护）开环-酸的9,12- anhydroerythronolide糖苷配基（的5）。
• 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
• Total Asymmetric Synthesis of a New 9,12-Anhydroerythronolide Aglycone
  作者：Sandrine Gerber-Lemaire、Simon W. Ainge、Cécile Glanzmann、Pierre Vogel

  DOI：10.1002/1522-2675(200202)85:2<417::aid-hlca417>3.0.co;2-1

  日期：2002.2

  Two novel, potentially antimicrobial erythronolide aglycon analogs ((-)-9 and (-)-30, respectively), which incorporate a large number of contiguous stereogenic centers, have been prepared by multistep synthesis from simple chirons. The chemistry presented demonstrates the power of the so-called 'naked sugars of the second acneration' approach. As for the sporeamicins, our macrolides are 9,12-anhydroerythronotides, yet presenting a higher degree of complexity due to additional functional groups.