3-[(3R,4S,5R)-2-benzyl-5-methyl-3-phenyl-1,2-oxazolidine-4-carbonyl]-1,3-oxazolidin-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 3-[(3R,4S,5R)-2-benzyl-5-methyl-3-phenyl-1,2-oxazolidine-4-carbonyl]-1,3-oxazolidin-2-one
• 化学式: C₂₁H₂₂N₂O₄
• 分子量: 366.417
• InChiKey: BUIFTGKVXDKVAV-LZQZEXGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methylmagnesium iodide 、 3-[(3R,4S,5R)-2-benzyl-5-methyl-3-phenyl-1,2-oxazolidine-4-carbonyl]-1,3-oxazolidin-2-one 以100%的产率得到(3R,4S,5R)-2-Benzyl-5-methyl-3-phenyl-isoxazolidine-4-carboxylic acid methyl ester
  参考文献：
  名称：

  Catalytic Enantioselective 1,3-Dipolar Cycloadditions between Nitrones and Alkenes Using a Novel Heterochiral Ytterbium(III) Catalyst

  摘要：

  DOI：

  10.1021/ja980702c
• 作为产物：
  描述：

  N-Benzylidenebenzylamine N-oxide 、 3-[(E)-2-丁酰基]-1,3-噁唑烷-2-酮 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 3-[(3R,4S,5R)-2-benzyl-5-methyl-3-phenyl-1,2-oxazolidine-4-carbonyl]-1,3-oxazolidin-2-one
  参考文献：
  名称：

  使用3,3'-双（2-恶唑基）-1,1'-bi-2-萘酚（BINOL-Box）配体，镧系元素催化的亚硝基不对称1,3-偶极环加成环烯烃

  摘要：

  合成了新的BINOL衍生的配体3,3'-双（2-恶唑基）-1,1'-bi-2-萘酚（BINOL-Box），在3,3'-碳上带有手性双恶唑啉购自市售的1，1'-联-2-萘酚（BINOL）。使用获得的新配体，我们发现N-亚苄基苄胺N-氧化物（2）与3-（（E）-2-丁烯酰基）-1,3-恶唑烷丁二酮（1）的不对称1,3-偶极环加成反应1）被BINOL-Box-scan络合物催化，以高收率，高非对映体和对映体选择性得到异恶唑烷3。例如，1和2的反应以6 mol％（S，R）-图7d和5摩尔％的钪（OTF）3复合物进行，得到内型-3作为与主要非对映体内：外的97：3的比例和87％ee值的内切在4埃分子筛存在下-产物。有趣的是，主要产品的绝对构型根据所用添加剂的种类而改变。

  DOI：

  10.1016/s0022-328x(00)00024-3

文献信息

• Enantio- and Diastereoselectivity in 1,3-Dipolar Cycloaddition Reactions of Nitrones with 3-Crotonoyl-2-oxazolidinone Catalyzed by Ni(II)- Binaphthyldiimine Complexes
  作者：Hiroyuki Suga、Akikazu Kakehi、Suketaka Ito、Hiroaki Sugimoto

  DOI：10.1246/bcsj.76.327

  日期：2003.2

  Chiral Ni(II)-1,1′-binaphthyl-2,2′-diimine complexes were found to be effective Lewis-acid catalysts for an asymmetric 1,3-dipolar cycloaddition reaction of N-benzylideneaniline N-oxide with 3-crotonoyl-2-oxazolidinone. In the presence of molecular sieves (4 A), when the chiral N,N′-bis(2,6-dichlorobenzylidene)-1,1′-binaphthyl-2,2′-diamine (BINIM-DC) and Ni(ClO4)2·6H2O were used to prepare the catalyst

  发现手性 Ni(II)-1,1'-联萘-2,2'-二亚胺配合物是有效的路易斯酸催化剂，用于 N-亚苄基苯胺 N-氧化物与 3-巴豆酰的不对称 1,3-偶极环加成反应-2-恶唑烷酮。在分子筛 (4 A) 存在下，当手性 N,N'-双(2,6-二氯亚苄基)-1,1'-联萘-2,2'-二胺 (BINIM-DC) 和 Ni(ClO4 )2·6H2O 用于制备催化剂，以内选择性（87:13 和高达 96:4）获得了高达 81% ee 的相应内环加合物。在类似条件下使用 N,N'-双（3-氯取代的 2-羟基亚苄基）衍生物作为配体显示出高外选择性（高达 95:5）和中等对映选择性。尽管几乎没有观察到非对映选择性，但获得了具有前景的对映选择性水平的内环加合物和外环加合物（高达 >
• Lanthanide-catalyzed endo- and enantioselective 1,3-dipolar cycloaddition reactions of nitrones with alkenes
  作者：Ana I. Sanchez-Blanco、Kurt V. Gothelf、Karl Anker Jørgensen

  DOI：10.1016/s0040-4039(97)10048-x

  日期：1997.11

  be dependent on the amount and type of molecular sieves added. The application of different chiral ligands in 1,3-dipolar cycloaddition reactions of a series of alkenes with nitrones catalyzed by Yb(OTf)3 or Sc(OTf)3 has been studied and it was found that high endo-selectivities and an ee's of up to 73% could be obtained by the use of Yb(OTf)3 and 2,6-bis[4(S)-isopropyl-2-oxazolidin-2-yl]pyridine (PyBOX)

  Yb（OTf）3或Sc（OTf）3催化烯烃与硝酮的1,3-偶极环加成反应，可高产率，高选择性地产生异恶唑烷。催化剂Yb（OTf）3在反应中引起高达94％de的高内选择性，而Sc（OTf）3显示出最高的速率加速。事实证明，Yb（OTf）3和Sc（OTf）3催化的反应的转化率和内选择性都取决于所添加分子筛的数量和类型。Yb（OTf）3或Sc（OTf）催化的一系列烯烃与硝酮的1,3-偶极环加成反应中不同手性配体的应用3已被研究并发现，高内-selectivities和的ee是高达73％可通过使用的Yb（OTF）获得的3和2,6-双[4（S） -异丙基-2-恶唑烷-2-基]吡啶（PyBOX）为手性配体。
• A switch of enantiofacial selectivity in chiral ytterbium-catalyzed 1,3-dipolar cycloaddition reactions
  作者：Mikako Kawamura、Shū Kobayashi

  DOI：10.1016/s0040-4039(99)00469-4

  日期：1999.4

  Synthesis of both enantiomers of the 1,3-dipolar cycloaddition adducts between nitrones and alkenes has been achieved using the same chiral ytterbium catalyst choosing achiral additives, nitrone and MS 4A.

  使用相同的手性y催化剂，选择非手性添加剂，硝酮和MS 4A，已经实现了在硝酮和烯烃之间的1，3-偶极环加成反应的两种对映异构体的合成。
• Palladium(II)-Catalyzed Asymmetric 1,3-Dipolar Cycloaddition of Nitrones to 3-Alkenoyl-1,3-oxazolidin-2-ones
  作者：Kazushige Hori、Hidehiko Kodama、Tetsuo Ohta、Isao Furukawa

  DOI：10.1021/jo981483g

  日期：1999.7.1

  obtained from the reaction of N-benzylidenemethylamine N-oxide and 3-crotonoyl-1,3-oxazolidin-2-one in 89% yield with 60% endo selectivity and 91% ee of the endo isomer. The cycloaddition of N-benzylidenebenzylamine N-oxide and 3-crotonoyl-1,3-oxazolidin-2-one afforded 3-((2-benzyl-5-methyl-3-phenylisoxazolidin-4-yl)carbonyl)-1,3-oxazolidin-2-one in 94% yield with 93% endo selectivity and 89% ee of the

  已经研究了手性膦钯 (II) 催化的硝酮不对称 1,3-偶极环加成反应生成 α,β-不饱和羧酸衍生物。在催化量的 [Pd(NCMe)2(S)-tolbinap}](BF4)2 [TolBINAP = 2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl] 存在下, 3-烯酰基-1,3-恶唑烷-2-酮作为偶极体与N-取代的N-亚苄基硝酮的反应已成功进行，以高产率和高对映选择性得到异恶唑烷衍生物。例如，3-((2,5-二甲基-3-苯基异恶唑烷-4-基)羰基)-1,3-恶唑烷-2-酮由N-亚苄基甲胺N-氧化物与3-巴豆酰- 1,3-恶唑烷-2-one 的产率为 89%，内向选择性为 60%，内向异构体的 ee 为 91%。N-亚苄基苄胺N-氧化物与3-巴豆酰-1的环加成，3-恶唑烷-2-one 以 94% 的收率和 93% 的内向选择性提供 3-((2-b
• Control of Diastereo- and Enantioselectivity in Metal-Catalyzed 1,3-Dipolar Cycloaddition Reactions of Nitrones with Alkenes. Experimental and Theoretical Investigations
  作者：Kurt V. Gothelf、Rita G. Hazell、Karl Anker Jørgensen

  DOI：10.1021/jo951204e

  日期：1996.1.1

  The scopes and limitations of the catalytic effects of achiral and chiral Mg(II) and Cu(II) complexes on the stereochemistry of the 1,3-dipolar cycloaddition reaction of nitrones with alkenes have been investigated. A remarkably high degree of endo-selectivity (endo/exo > 20) is induced in the 1,3-dipolar cycloaddition reaction by the presence of a catalytic amount of, especially, a Mg(II)-phenanthroline complex. The diastereochemical assignment of the product is confirmed by an X-ray crystallographic determination of the structure of the exo-isoxazolidine. By the reaction of an alkene bearing a chiral auxiliary, with different nitrones and a catalytic amount of the Mg(II)-phenanthroline complex, one of four possible diastereomers of the isoxazolidines is exclusively formed. The absolute stereochemistry of this product is also assigned by an X-ray crystallographic investigation. The presence of a catalytic amount of a chiral Mg(II)-bisoxazoline complex in the 1,3-dipolar cycloaddition reaction leads to high endo-selectivity and occasionally with an ee > 80%. The reaction mechanism of the Mg(II)-catalyzed reaction is discussed on the basis of the experimental results and semiempirical quantum chemical calculations. The calculations are used to account for the catalytic effect of the Mg(II)-ligand complexes and to determine transition state energies for both the uncatalyzed and Mg(II)-ligand-catalyzed reactions.