(S)-(2u,6l)-6-methyl-3-(1-methylethyl)-2-(phenylmethyl)-1,3,2-oxazaphosphorinane 2-oxide | 145124-62-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧氮杂膦
• 英文名称: (S)-(2u,6l)-6-methyl-3-(1-methylethyl)-2-(phenylmethyl)-1,3,2-oxazaphosphorinane 2-oxide
• 英文别名: (2R,6S)-2-benzyl-6-methyl-3-propan-2-yl-1,3,2lambda5-oxazaphosphinane 2-oxide；(2R,6S)-2-benzyl-6-methyl-3-propan-2-yl-1,3,2λ5-oxazaphosphinane 2-oxide
• CAS: 145124-62-5
• 化学式: C₁₄H₂₂NO₂P
• 分子量: 267.308
• InChiKey: PQQJUAGJLXLJRK-SCLBCKFNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-(2u,6l)-6-methyl-3-(1-methylethyl)-2-(phenylmethyl)-1,3,2-oxazaphosphorinane 2-oxide 在 叔丁基锂 作用下， 反应 1.5h， 生成 (S)-(2u,6l,1'l)-2-(1',2'-diphenylethyl)-3-(1-methylethyl)-6-methyl-1,3,2-oxazaphosphorinane 2-oxide
  参考文献：
  名称：

  Alkylations of Chiral, Phosphoryl- and Thiophosphoryl-Stabilized Carbanions

  摘要：

  A general method for the preparation of enantiomerically enriched phosphonic acids and phosphonates with three different a-substitution patterns (aryl, alkyl, and alkoxy) has been developed. Anions derived from enantiomerically enriched thiophosphonamidates (2-thioxo-1,3,2-oxazaphosphorinanes) underwent smooth electrophilic substitutions with excellent diastereoselectivity for both cis and trans stereoisomers. Highly enantioselective synthesis of alpha-alkoxyphosphonates in either antipodal form can be achieved by the employment of highly diastereoselective alkylation with anions derived from the corresponding P-methoxymethyl analogs in the presence of HMPA or PMDTA. Implications for the aggregation states and reactive conformations of the anions are discussed.

  DOI：

  10.1021/ja00153a009
• 作为产物：
  描述：

  (S)-N-(1-methylethyl)-3-hydroxybutyramide 在 硼烷四氢呋喃络合物 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 29.5h， 生成 (S)-(2u,6l)-6-methyl-3-(1-methylethyl)-2-(phenylmethyl)-1,3,2-oxazaphosphorinane 2-oxide
  参考文献：
  名称：

  Alkylations of Chiral, Phosphoryl- and Thiophosphoryl-Stabilized Carbanions

  摘要：

  A general method for the preparation of enantiomerically enriched phosphonic acids and phosphonates with three different a-substitution patterns (aryl, alkyl, and alkoxy) has been developed. Anions derived from enantiomerically enriched thiophosphonamidates (2-thioxo-1,3,2-oxazaphosphorinanes) underwent smooth electrophilic substitutions with excellent diastereoselectivity for both cis and trans stereoisomers. Highly enantioselective synthesis of alpha-alkoxyphosphonates in either antipodal form can be achieved by the employment of highly diastereoselective alkylation with anions derived from the corresponding P-methoxymethyl analogs in the presence of HMPA or PMDTA. Implications for the aggregation states and reactive conformations of the anions are discussed.

  DOI：

  10.1021/ja00153a009

文献信息

• Alkylation of Chiral, Phosphorus-Stabilized Carbanions: Substituent Effects on the Alkylation Selectivity
  作者：Scott E. Denmark、Chien-Tien Chen

  DOI：10.1021/jo00090a004

  日期：1994.6

  The alkylation of a series of enantiomerically pure cis and trans 3-substituted 2-benzyl-6-methyl-1,3,2-oxazaphosphorinane 2-oxides was found to be sensitive to the bulk of the N-substituents.
• Alkylations of Chiral, Phosphoryl- and Thiophosphoryl-Stabilized Carbanions
  作者：Scott E. Denmark、Chien-Tien Chen

  DOI：10.1021/ja00153a009

  日期：1995.12

  A general method for the preparation of enantiomerically enriched phosphonic acids and phosphonates with three different a-substitution patterns (aryl, alkyl, and alkoxy) has been developed. Anions derived from enantiomerically enriched thiophosphonamidates (2-thioxo-1,3,2-oxazaphosphorinanes) underwent smooth electrophilic substitutions with excellent diastereoselectivity for both cis and trans stereoisomers. Highly enantioselective synthesis of alpha-alkoxyphosphonates in either antipodal form can be achieved by the employment of highly diastereoselective alkylation with anions derived from the corresponding P-methoxymethyl analogs in the presence of HMPA or PMDTA. Implications for the aggregation states and reactive conformations of the anions are discussed.