(4S)-2,2,5,5-tetramethyl-4-phenylmethyloxazolidine | 144899-42-3

• 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: (4S)-2,2,5,5-tetramethyl-4-phenylmethyloxazolidine
• 英文别名: (S)-4-benzyl-2,2,5,5-tetramethyloxazolidine；4-benzyl-2,2,5,5-tetramethyloxazolidine；(4S)-4-benzyl-2,2,5,5-tetramethyl-1,3-oxazolidine
• CAS: 144899-42-3
• 化学式: C₁₄H₂₁NO
• 分子量: 219.327
• InChiKey: VCQROYSNELFEJO-LBPRGKRZSA-N

物化性质

• 沸点：
  289.7±28.0 °C(Predicted)
• 密度：
  0.949±0.06 g/cm3(Predicted)
• 溶解度：
  very sol in most organic solvents; decomposition occurs in protic solvents.

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S)-2,2,5,5-tetramethyl-4-phenylmethyloxazolidine 在 DMd 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 24.0h， 生成 [S-(2S,3R)]-2,2,5,5-tetramethyl-3-[(2,3-dimethyloxiranyl)carbonyl]-4-phenylmethyloxazolidine
  参考文献：
  名称：

  Opposite π-Face Selectivity for the DMD and m-CPBA Epoxidations of Chiral 2,2-Dimethyloxazolidine Derivatives of Tiglic Amides:  Control by Steric Interactions versus Hydrogen Bonding

  摘要：

  A high extent but opposite sense in the diastereoselectivity has been observed for the DMD and m-CPBA epoxidations of the optically active tiglic amides (S)-1 with 2,2-dimethyloxazolidines as chiral auxiliaries, This unprecedented reversed pi-facial differentiation for these two peroxidic oxidants is rationalized in terms of like (lk) and unlike (ul) transition structures: For DMD, steric interactions dominate, such that the unlike transition structure is favored, while for m-CPBA, hydrogen bonding effects overcome these steric repulsions and the like one is preferred.

  DOI：

  10.1021/ol990405s
• 作为产物：
  描述：

  L-苯丙氨酸甲酯 在 对甲苯磺酸 作用下， 反应 12.0h， 生成 (4S)-2,2,5,5-tetramethyl-4-phenylmethyloxazolidine
  参考文献：
  名称：

  New chiral auxiliaries based on conformation control, a C2-symmetric 2,2-dimethylimidazolidine and 4-chiral, 2,2-dialkyloxazolidines. Synthesis and conformational analysis of acrylamide derivatives

  摘要：

  New chirality-controlling auxiliaries, a C2-symmetric 2,2-dimethylimidazolidine and 4-chiral 2,2-dialkyloxazolidines, are readily prepared from a C2-SYMMetriC 1,2-ethanediamine and naturally occurring alpha-amino acids, respectively. Conformational analysis of their N-acryloyl derivatives has been carried out on the basis of dynamic H-1 NMR spectroscopy and molecular mechanics calculations using MM2 program. Proper choice of the substituents at 2-, 4-, and 5-positions, in the oxazolidine cases, leads to the most effective chiral shielding of a diastereotopic acryloyl face.

  DOI：

  10.1016/s0040-4020(01)89439-4

文献信息

• Synthesis of Tertiary β-Hydroxy Amides by Enolate Additions to Acylsilanes
  作者：Robert B. Lettan、Troy E. Reynolds、Chris V. Galliford、Karl A. Scheidt

  DOI：10.1021/ja065605v

  日期：2006.12.1

  synthesis of tertiary β-hydroxy amides from acylsilanes, acetamides, and electrophiles is described. The addition of amide enolates to acylsilanes generates β-silyloxy homoenolate reactivity by undergoing a 1,2-Brook rearrangement. These unique nucleophiles formed in situ can then undergo smooth addition to alkyl halides, aldehydes, and ketones. Enolates derived from amides are crucial for the success

  描述了从酰基硅烷、乙酰胺和亲电试剂合成叔 β-羟基酰胺。通过进行 1,2-布鲁克重排，将酰胺烯醇化物添加到酰基硅烷中会产生 β-甲硅烷氧基均烯醇化物反应性。这些在原位形成的独特亲核试剂可以顺利地加入到卤代烷、醛和酮中。源自酰胺的烯醇化物对于该过程的成功至关重要，因为酮烯醇化物受到 β-碳负离子内部返回到羰基碳上的影响。使用光学活性酰胺烯醇化物可提供具有良好非对映选择性 (≥10:1) 的 β-羟基酰胺产品。
• Amide Enolate Additions to Acylsilanes: In Situ Generation of Unusual and Stereoselective Homoenolate Equivalents
  作者：Robert B. Lettan、Chris V. Galliford、Chase C. Woodward、Karl A. Scheidt

  DOI：10.1021/ja808811u

  日期：2009.7.1

  The synthesis of beta-hydroxy carbonyl compounds is an important goal due to their prevalence in bioactive molecules. A novel approach to construct these structural motifs involves the multicomponent reaction of acylsilanes, amides, and electrophiles. The addition of amide enolates to acylsilanes generates beta-silyloxy homoenolate reactivity by undergoing a 1,2-Brook rearrangement. These unique nucleophiles

  β-羟基羰基化合物的合成是一个重要的目标，因为它们普遍存在于生物活性分子中。一种构建这些结构基序的新方法涉及酰基硅烷、酰胺和亲电试剂的多组分反应。通过进行 1,2-布鲁克重排，将酰胺烯醇化物添加到酰基硅烷中会产生 β-甲硅烷氧基均烯醇化物反应性。这些在原位形成的独特亲核试剂随后可以与卤代烷、醛、酮和亚胺进行加成。通过将这些同烯醇化物添加到 N-二苯基膦亚胺中而产生的 γ-氨基-β-羟基酰胺产物具有出色的非对映选择性（> 或 = 20:1），并且可以有效地转化为高价值的 γ-内酰胺。最后，
• Effective Enantiocontrol in Conjugate Additions of Organocuprates. Highly Selective 1,5-Chiral Induction in the Conjugate Additions of Cuprates to .alpha.,.beta.-Unsaturated Amide Derivatives of 2,2-Dimethyloxazolidine Chiral Auxiliaries
  作者：Shuji Kanemasa、Hiroyuki Suenaga、Kenjiro Onimura

  DOI：10.1021/jo00102a018

  日期：1994.11

  alpha,beta-Unsaturated amide derivatives of 2,2-dimethyloxazolidines, developed as new chirality-controlling auxiliaries based on the restricted rotation of the amide linkage, have been applied to the enantiocontrol of conjugate additions of lithium and magnesium cuprates. High selectivities of 1,5-chiral inductions are attained, indicating their promising synthetic potential in asymmetric synthesis. The diastereofacial selectivities depend upon the efficiency of steric shielding by the 4-substituent of the chiral auxiliary, and the reaction of (S)-4-benzyl-3-[(E)-2-butenoyl]-2,2,5,5-tetramethyloxazolidine with Ph(2)CuMgBr.MgBrI is exclusively lk-1,5-inductive. Use of organolithium and organomagnesium show opposite low selectivities. It is concluded that the stereochemistry of cuprate conjugate addition is determined at the step of formation of the d,pi* type charge transfer complexes.
• Asymmetric anti-selective aldol reactions of titanium Z-enolates derived from N-alkylideneglycinamides bearing a 2,2-dimethyloxazolidine chiral controller
  作者：Shuji Kanemasa、Takashi Mori、Akira Tatsukawa

  DOI：10.1016/s0040-4039(00)61414-4

  日期：1993.12

  Asymmetric aldol reactions of titanium Z-enolates of N-diphenylmethylene derivatives of glycinamides derived from (4S)-2,2-dimethyloxazolidine chiral auxiliaries are highly ul,ul-1,4-inductive. Hydrolytic removal of the chiral auxiliary from the aldol adducts provide optically active anti-isomers of alpha-amino-beta-hydroxy acids with 2R-absolute configuration.
• Regio- and Stereoselective Addition of Allylmetal Reagents to Pyridinium−π and Quinolinium−π Complexes
  作者：Shinji Yamada、Mai Inoue

  DOI：10.1021/ol070168q

  日期：2007.4.1

  Regio- and stereoselective allylation of pyridinium and quinolinium salts was performed by the addition of allylindium and allyltributyltin reagents toward intermediary cation-pi complexes. The reaction with allylindium and allyltributyltin reagents afforded a 1,2-adduct, whereas the addition of a prenylindium reagent gave a 1,4-adduct with good regio- and stereoselectivities. X-ray structural analysis, H-1 NMR studies, and DFT calculations elucidated the intermediary cation-pi complex formation with face-to-face orientation.