(2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-5-cyclohexen-1-one | 188308-05-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-5-cyclohexen-1-one
• 英文别名: (2R,3S,4S)-4-tert-butyldimethylsilyloxy-2,3-epoxy-5-cyclohexen-1-one；(1R,5S,6S)-5-[tert-butyl(dimethyl)silyl]oxy-7-oxabicyclo[4.1.0]hept-3-en-2-one
• CAS: 188308-05-6
• 化学式: C₁₂H₂₀O₃Si
• 分子量: 240.374
• InChiKey: SMCFMNSSLNZXMJ-GARJFASQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-5-cyclohexen-1-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 吡啶 、 4-二甲氨基吡啶 、 copper(l) iodide 、 三苯胂 、 氢氟酸 、 碘 、 二乙胺 作用下， 以 四氢呋喃 、 四氯化碳 、 乙腈 为溶剂， 反应 25.0h， 生成 5-羟基-3-甲基-(1R,5S,6R)-7-氧杂双环[4.1.0]庚-3-烯-2-酮
  参考文献：
  名称：

  The First Synthesis of (−)-Asperpentyn and Efficient Syntheses of (+)-Harveynone, (+)-Epiepoformin and (−)-Theobroxide

  摘要：

  A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexane natural products has been developed. The enantioselective syntheses of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-silyl migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid. A thus derived alpha -iodoenone was subjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar strategy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)-harveynone. By selective reduction of (-)-theobroxide, (+)-epiepoformin was also prepared in enantiopure form and similarly, stereoselective reduction of (+)-harveynone completed the first enantioselective synthesis of (-)-asperpentyn, another natural compound with antimicrobial activity.

  DOI：

  10.1002/1521-3765(20001103)6:21<3991::aid-chem3991>3.3.co;2-m
• 作为产物：
  描述：

  (3aR,7R,7aS)-7-hydroxy-2,2-dimethyltetrahydrobenzo[d][1,3]dioxol-5(6H)-one 在 咪唑 、 sodium hydroxide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 (2R,3S,4S)-4-[(tert-Butyldimethylsilyl)oxy]-2,3-epoxy-5-cyclohexen-1-one
  参考文献：
  名称：

  The First Synthesis of (−)-Asperpentyn and Efficient Syntheses of (+)-Harveynone, (+)-Epiepoformin and (−)-Theobroxide

  摘要：

  A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexane natural products has been developed. The enantioselective syntheses of (-)-theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O-silyl migration between trans-hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid. A thus derived alpha -iodoenone was subjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar strategy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)-harveynone. By selective reduction of (-)-theobroxide, (+)-epiepoformin was also prepared in enantiopure form and similarly, stereoselective reduction of (+)-harveynone completed the first enantioselective synthesis of (-)-asperpentyn, another natural compound with antimicrobial activity.

  DOI：

  10.1002/1521-3765(20001103)6:21<3991::aid-chem3991>3.3.co;2-m

文献信息

• Strictly Regiocontrolled α-Monosubstitution of Cyclic Carbonyl Compounds with Alkynyl and Alkyl Groups via Pd-Catalyzed Coupling of Cyclic α-Iodoenones with Organozincs
  作者：Ei-ichi Negishi、Ze Tan、Show-Yee Liou、Baiqiao Liao

  DOI：10.1016/s0040-4020(00)00864-4

  日期：2000.12

  derivatives readily undergo Pd-catalyzed cross coupling with α-iodoenones. Although (s-Bu)2Zn also undergoes Pd-catalyzed cross coupling, only the n-Bu-substituted products were obtained. α-Benzylation and α-homobenzylation can proceed satisfactorily, whereas allylzinc and propargylzinc derivatives undergo only addition to the carbonyl group. Although some promising results have been obtained in α-homoallylation

  已优化了Pd催化的环状α-碘烯酮（如2-碘-2-环己烯酮）与炔基锌的交叉偶联条件。使用三（邻-呋喃基）膦（TFP）作为配体和使用DMF作为溶剂已导致以优异的产率形成α-炔基酮。该最优化的方法已用于高产率合成（±）-harveynone和（±）-tricholomenynA。对使用烷基锌的相关α-烷基化反应的研究揭示了以下内容。甲基锌和伯烷基锌衍生物容易与α-碘烯酮进行Pd催化的交叉偶联。尽管（s -Bu）2 Zn也经历Pd催化的交叉偶联，但只有n获得-Bu-取代的产物。α-苄基化和α-高苄基化可以令人满意地进行，而烯丙基锌和炔丙基锌衍生物仅在羰基上加成。尽管已经在α-均烯丙基化和α-均丙炔化中获得了一些有希望的结果，但是这些反应仍需要进一步改善。
• Total synthesis of (+)-epiepoformin, (+)-epiepoxydon and (+)-bromoxone employing a useful chiral building block, ethyl (1R,2S)-5,5-ethylenedioxy-2-hydroxycyclohexanecarboxylate
  作者：Toru Tachihara、Takeshi Kitahara

  DOI：10.1016/s0040-4020(03)00119-4

  日期：2003.3

  Enantioselective total synthesis of (+)-epiepoformin 1, (+)-epiepoxydon 2 and (+)-bromoxone 3 using a chiral building block, ethyl (1R,2S)-5,5-ethylenedioxy-2-hydroxycyclo- hexanecarboxylate 6, is described. Since the synthesis afforded intermediates 18, 2 and 25, it accomplished a formal synthesis of (−)-theobroxide 19, (−)-phyllostine 22, (+)-herveynone 27 and (−)-asperpentyn 28. The usefulness of

  使用手性结构单元（1 R，2 S）-5,5-乙撑二氧基-2-羟基环己烷甲酸乙酯对映体选择性合成（+）-表二甲双胍1，（+）-表氧双酚2和（+）-溴酮3参照图6进行说明。由于合成，得到中间体18，2和25，它完成的正式合成（ - ） - theobroxide 19，（ - ） - phyllostine 22，（+） - herveynone 27和（ - ） - asperpentyn 28。证明了6对于合成天然环氧环己烯衍生物的有用性。
• Temporary thio-derivatization in the synthesis of (+)-4-acetylbromoxone
  作者：Aisling O’Byrne、Steven O’Reilly、Catherine Tighe、Paul Evans、Laura Ciuffini、M. Gabriella Santoro

  DOI：10.1016/j.tetlet.2012.08.101

  日期：2012.10

  A stereocontrolled synthesis of the marine natural products (+)-bromoxone (1) and (+)-4-acetylbromoxone (2) is reported. The sequence features the enzymatic kinetic resolution of 4-hydroxycyclohexenone (6) via its S-benzyl adduct. Thereafter, a base-mediated elimination–silylation generated an optically active (−)-4S-4-tert-butyldimethylsilyoxycyclohexenone (5), which then underwent diastereoselective

  bromoxone（ -海洋天然产物（+）的立体控制合成1 4- acetylbromoxone（ - ）和（+）2被报告）。该序列具有4-羟基环己烯酮（6）通过其S-苄基加合物的酶促动力学拆分特征。此后，碱介导的消除-甲硅烷基化反应生成了旋光性（-）-4 S -4-叔丁基二甲基甲硅烷氧基环己烯酮（5），然后进行非对映选择性环氧化。Saegusa-Ito氧化能够形成相应的α，β-不饱和酮13。溴化消除并随后除去硅保护基，得到（+）-溴酮（1），将其转化为（+）-（4 S，5 R，6 R）-4-乙酰氧基-2-溴-5,6-环氧环己基-2-烯酮（2）[（+）-4-乙酰基溴酮]。使用萤光素酶基因报告基因测定法，ED 50对NFκB的抑制作用为9μM。
• Asymmetric synthesis of chiral cycloalkenone derivatives <i>via</i> palladium catalysis
  作者：Barry M. Trost、James T. Masters、Jean-Philip Lumb、Dahlia Fateen

  DOI：10.1039/c3sc53250j

  日期：——

  Palladium-catalyzed oxidative desymmetrization enables the efficient synthesis of both enantioenriched cycloalkenone building blocks and diverse epoxyquinoid natural products.

  钯催化的氧化去对称化反应可有效合成手性富集的环烯酮构建块和多样的环氧醌天然产物。
• Sonogashira Coupling of 2-Iodo-2-cycloalkenones:  Synthesis of (+)- and (−)-Harveynone and (−)-Tricholomenyn A
  作者：Michael W. Miller、Carl R. Johnson

  DOI：10.1021/jo962295y

  日期：1997.3.1