(2S,3'R)-3'-p-tolyl-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (2S,3'R)-3'-p-tolyl-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one
• 英文别名: (2S,3R)-2-(4-methylbenzylidene)-1-tetralone oxide；3'-(4-methphenyl)-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one；(2S,3'R)-3'-(4-methylphenyl)spiro[3,4-dihydronaphthalene-2,2'-oxirane]-1-one
• 化学式: C₁₈H₁₆O₂
• 分子量: 264.324
• InChiKey: BGGAPEMJYSEKNM-QZTJIDSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-p-methylbenzylidene-1-tetralone 在 叔丁基过氧化氢 、 [(Me₃Si)₂N]₃Yb(μ-Cl)Li(THF)₃ 、 (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以98%的产率得到(2S,3'R)-3'-p-tolyl-3,4-dihydro-1H-spiro[naphthalene-2,2'-oxiran]-1-one
  参考文献：
  名称：

  Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Amides [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ with Phenoxy-Functionalized Chiral Prolinols

  摘要：

  A simple and efficient catalytic enantioselective epoxidation of alpha,beta-unsaturated ketones has been successfully developed, which was catalyzed by rare-earth metal amides [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) (RE = Yb (1), La (2), Sm (3), Y (4), Lu (5)) in the presence of phenoxy-functionalized chiral prolinols at room temperature using tert-butylhydroperoxide (TBHP) as the oxidant. The combination of an Yb-based amide 1 and a chiral proligand (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol) performed very well, and both the yields and the enantiomeric excess of the chiral epoxides reached up to 99% and 99% ee.

  DOI：

  10.1021/acs.orglett.5b00833

文献信息

• Mononuclear Nonheme Iron(III)‐Iodosylarene and High‐Valent Iron‐Oxo Complexes in Olefin Epoxidation Reactions
  作者：Bin Wang、Yong‐Min Lee、Mi Sook Seo、Wonwoo Nam

  DOI：10.1002/anie.201505796

  日期：2015.9.28

  High‐spin iron(III)‐iodosylarene complexes are highly reactive in the epoxidation of olefins, in which epoxides are formed as the major products with high stereospecificity and enantioselectivity. The reactivity of the iron(III)‐iodosylarene intermediates is much greater than that of the corresponding iron(IV)‐oxo complex in these reactions. The iron(III)‐iodosylarene species—not high‐valent iron(IV)‐oxo

  高自旋铁（III）-碘杂芳烃配合物在烯烃的环氧化反应中具有很高的反应活性，其中环氧化物是主要产物，具有高立体选择性和对映选择性。在这些反应中，铁（III）-碘亚芳基中间体的反应性比相应的铁（IV）-氧代络合物大。铁（III）-碘亚芳基物质（不是高价铁（IV）-氧和铁（V）-氧）也被证明是催化烯烃环氧化反应中的活性氧化剂。鉴于长期以来关于氧化反应中一种氧化剂与多种氧化剂假设的争论，对本研究结果进行了讨论。
• Lanthanide complexes combined with chiral salen ligands: application in the enantioselective epoxidation reaction of α,β-unsaturated ketones
  作者：Xuexiu Xia、Chengrong Lu、Bei Zhao、Yingming Yao

  DOI：10.1039/c9ra01529a

  日期：——

  1,2-diphenyl-1,2-ethanediamine) were employed in the enantioselective epoxidation of α,β-unsaturated ketones. It was found that the salen–La complex shows the highest efficiency and enantioselectivity. A relatively broad scope of α,β-unsaturated ketones was investigated, and excellent yields (up to 99%) and moderate to good enantioselectivities (37–87%) of the target molecules were achieved.

  容易获得的镧系酰胺 Ln[N(SiMe 3 ) 2 ] 3 (Ln = Nd ( 1 ), Sm ( 2 ), Eu ( 3 ), Yb ( 4 ), La ( 5 )) 与手性 salen 配体 H 2结合La (( S , S )-N , N'-二- ( 3,5-二取代的亚水杨基)-1,2-环己二胺)和H 2 Lb ( ( S , S ) -N , N'-二-(3,5-二取代-水杨基)-1,2-二苯基-1,2-乙二胺)用于α,β-不饱和酮的对映选择性环氧化。结果发现，salen-La 配合物表现出最高的效率和对映选择性。研究了相对广泛的 α,β-不饱和酮，并实现了目标分子的优异产率（高达 99%）和中等至良好的对映选择性（37-87%）。
• Bioinspired Manganese and Iron Complexes with Tetradentate N Ligands for the Asymmetric Epoxidation of Olefins
  作者：Xiaoe Wang、Chengxia Miao、Shoufeng Wang、Chungu Xia、Wei Sun

  DOI：10.1002/cctc.201300102

  日期：2013.8

  and iron complexes with the tetradentate N ligand (1R,2R)‐N,N'‐dimethyl‐N,N'‐bis(1‐methyl‐2‐benzimidazolylmethyl)cyclohexane‐1,2‐diamine have been synthesized and characterized. The crystal structure of the manganese complex demonstrates a cis‐α configuration. Both the manganese and iron complexes are active catalysts for the asymmetric epoxidation of olefins with H2O2 as an oxidant and acetic acid as

  合成了具有四齿N配体（1 R，2 R）-N，N'-二甲基-N，N'-双（1-甲基-2-苯并咪唑基甲基）环己烷-1,2-二胺的锰和铁配合物和特点。锰配合物的晶体结构表现出顺-α构型。锰和铁络合物都是用于烯烃的不对称环氧化的活性催化剂，其中H 2 O 2为氧化剂，乙酸为添加剂。在-20°C时，观察到高达96％ee的α，β-不饱和酮的环氧化。
• Asymmetric phase transfer Darzens reactions catalyzed by d-glucose- and d-mannose-based chiral crown ethers
  作者：Zsolt Rapi、Péter Bakó、György Keglevich、Áron Szöllősy、László Drahos、Adrienn Botyánszki、Tamás Holczbauer

  DOI：10.1016/j.tetasy.2012.04.006

  日期：2012.4

  and d-mannose-based crown ethers 1 and 2 as the catalyst. The use of d-glucose-based lariat ether 1 as the catalyst gave the best results. The reaction of 4-phenyl-α-chloroacetophenone, 2-chloro-1-tetralone, and 2-chloro-1-indanone with various aromatic aldehydes afforded the corresponding aromatic α,β-epoxyketones in moderate to high enantiomeric excess (ee up to 96%) under mild reaction conditions

  液相-液相不对称Darzens缩合反应是在基于d-葡萄糖和d-甘露糖的冠醚1和2的存在下进行的。使用基于d-葡萄糖的套​​索状醚1作为催化剂可获得最佳结果。4-苯基-α-氯乙酰苯酮，2-氯-1-四氢萘酮和2-氯-1-茚满酮与各种芳族醛的反应可得到相应的芳族α，β-环氧酮，其对映体过量至中度对映体过量（ee最高可达96％）在温和的反应条件下。用作反应物的苯甲醛的取代基对化学收率和对映体过量有重大影响。一些环氧酮产品的绝对构型是通过单晶X射线分析确定的。
• Synthesis and stereochemistry of the epoxides of 2-arylmethylidene-1-tetralones
  作者：Waldemar Adam、Judit Halász、Zsigmond Jámbor、Albert Lévai、Csaba Nemes、Tamás Patonay、Gábor Tóth

  DOI：10.1039/p19960000395

  日期：——

  Oxidation of both the E and Z isomers of the 2-arylmethylidene-1-tetralones 1 by alkaline hydrogen peroxide afforded the spiroepoxides trans-2a-g as sole products in high yields. In contrast, the dimethyldioxirane epoxidation of the E isomers la-g gave the corresponding trans spiroepoxides in good yields, while the Z isomers la,c,e yielded the respective cis spiroepoxides in moderate yields, Epoxidation of(Z)-1a,c,e by m-chloroperoxybenzoic acid yielded ca. 6: 1 mixtures of cis-2a,c,e and trans-2a,c,e spiroepoxides, Separation of the isomeric epoxides was achieved by silica gel chromatography and their structures, relative configurations and stereochemistry were elucidated by NMR spectroscopy.