(S)-4-benzyl-3-methoxyacetyl-2,2,5,5-tetramethyloxazolidine | 171736-91-7

• 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: (S)-4-benzyl-3-methoxyacetyl-2,2,5,5-tetramethyloxazolidine
• 英文别名: 1-[(4S)-4-benzyl-2,2,5,5-tetramethyl-1,3-oxazolidin-3-yl]-2-methoxyethanone
• CAS: 171736-91-7
• 化学式: C₁₇H₂₅NO₃
• 分子量: 291.39
• InChiKey: RTWFDAGBOXPHOU-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 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：

  巴豆酸甲酯 、 (S)-4-benzyl-3-methoxyacetyl-2,2,5,5-tetramethyloxazolidine 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以50%的产率得到(S)-4-benzyl-3-<2-methoxy-3-methyl-4-(methoxycarbonyl)butanoyl>-2,2,5,5-tetramethyloxazolidine
  参考文献：
  名称：

  High enantiocontrol of michael additions by use of 2:2-dimethyloxazolidine chiral auxiliaries. Exclusively ul,lk-1,4-inductive michael additions of the lithium (z)-enolate of (s)-4-benzyl-2,2,5,5-tetramethyl-3-propanoyl-oxazolidine to α,β-unsaturated esters

  摘要：

  The lithium (Z)-enolate generated from the propanamide of (S)-4-benzyl-2,2,5,5-tetramethyloxazolidine undergoes highly lk-1,4/anti-selective Michael additions to alpha,beta-unsaturated ester and amide accepters. However, only poor selectivities result when either the lithium (Z)enolates of an oxazolidine methoxyacetamide derivative or the oxazolidine alpha,beta-unsaturated amide accepters are used. The observed high chiral inductions in the former cases are based on the facts that syn-conformation of the enolate is involved in the transition state where the enolate and oxazolidine planes are coplanar, and that the diastereoface remote from the 4-shielding substituent of the auxiliary is open for the attack of acceptor molecules.

  DOI：

  10.1016/0040-4020(95)00623-g
• 作为产物：
  描述：

  甲氧基乙酰氯 、 (4S)-2,2,5,5-tetramethyl-4-phenylmethyloxazolidine 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以71%的产率得到(S)-4-benzyl-3-methoxyacetyl-2,2,5,5-tetramethyloxazolidine
  参考文献：
  名称：

  High enantiocontrol of michael additions by use of 2:2-dimethyloxazolidine chiral auxiliaries. Exclusively ul,lk-1,4-inductive michael additions of the lithium (z)-enolate of (s)-4-benzyl-2,2,5,5-tetramethyl-3-propanoyl-oxazolidine to α,β-unsaturated esters

  摘要：

  The lithium (Z)-enolate generated from the propanamide of (S)-4-benzyl-2,2,5,5-tetramethyloxazolidine undergoes highly lk-1,4/anti-selective Michael additions to alpha,beta-unsaturated ester and amide accepters. However, only poor selectivities result when either the lithium (Z)enolates of an oxazolidine methoxyacetamide derivative or the oxazolidine alpha,beta-unsaturated amide accepters are used. The observed high chiral inductions in the former cases are based on the facts that syn-conformation of the enolate is involved in the transition state where the enolate and oxazolidine planes are coplanar, and that the diastereoface remote from the 4-shielding substituent of the auxiliary is open for the attack of acceptor molecules.

  DOI：

  10.1016/0040-4020(95)00623-g

文献信息

• Chirality control by the aid of 2:2-dimethyloxazolidine chiral auxiliaries. Highly 1:4-chiral inductive asymmetric alkylations of amide enolates
  作者：Shuji Kanemasa、Koichi Ueno、Kenjiro Onimura、Takashi Kikukawa、Hidetoshi Yamamoto

  DOI：10.1016/0040-4020(95)00624-h

  日期：1995.9

  The propanamide and methoxyacetamide derivatives of (S)-4-benzyl-2,2,5,5-tetramethyloxazolidine, a new chirality controlling auxiliary based on the restricted rotation around amide bond, generate chiral lithium Z-enolates by lithiation. They undergo highly lk-1,4 and ul-1,4-inductive alkylations with a variety of alkylating reagents, respectively. The diastereotopic face participated in the reactions

  （S）-4-苄基-2,2,5,5-四甲基恶唑烷的丙酰胺和甲氧基乙酰胺衍生物是一种新的手性控制助剂，其基于绕酰胺键的受限旋转，通过锂化生成手性Z-烯醇锂。它们分别通过各种烷基化试剂进行高度lk -1,4和ul -1,4-诱导烷基化。参与反应的非对映体面是在顺式构象中远离恶唑烷的4-保护取代基的面。过渡态的烯醇双键和恶唑烷平面之间的共面性可能是观察到的优异选择性的主要因素。