(S)-(2u,6l)-3-(1,1-Dimethylethyl)-6-methyl-2-(2-propenyl)-1,3,2-oxazaphosphorinane 2-oxide | 172909-95-4

• 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)-3-(1,1-Dimethylethyl)-6-methyl-2-(2-propenyl)-1,3,2-oxazaphosphorinane 2-oxide
• 英文别名: (2R,6S)-3-tert-butyl-6-methyl-2-prop-2-enyl-1,3,2lambda5-oxazaphosphinane 2-oxide；(2R,6S)-3-tert-butyl-6-methyl-2-prop-2-enyl-1,3,2λ5-oxazaphosphinane 2-oxide
• CAS: 172909-95-4
• 化学式: C₁₁H₂₂NO₂P
• 分子量: 231.275
• InChiKey: RADGBBRUAQHVPD-ZUZCIYMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  2-环庚烯-1-酮 、 (S)-(2u,6l)-3-(1,1-Dimethylethyl)-6-methyl-2-(2-propenyl)-1,3,2-oxazaphosphorinane 2-oxide 在 copper(l) iodide 、 正丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 1.0h， 生成 1-[1-((S)-3-tert-Butyl-6-methyl-2-oxo-2λ⁵-[1,3,2]oxazaphosphinan-2-yl)-allyl]-cyclohept-2-enol 、 (S)-(2u,6l,3''l)-(1'E)-2-<3'-(3''-Oxocycloheptyl)-1'-propenyl>-3-(1,1-dimethylethyl)-6-methyl-1,3,2-oxazaphosphorinane 2-oxide 、 (S)-(2u,6l,3''u)-(1'E)-2-<3'-(3''-Oxocycloheptyl)-1'-propenyl>-3-(1,1-dimethylethyl)-6-methyl-1,3,2-oxazaphosphorinane 2-oxide
  参考文献：
  名称：

  Asymmetric Michael Addition Reaction of Phosphorus-Stabilized Allyl Anions with Cyclic Enones

  摘要：

  The asymmetric Michael addition reaction of chirally modified P-allyl anions derived from enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides has been investigated with cyclic enones. The racemic 1,3,2-oxazaphosphorinane 2-oxide 3 has been shown to be extremely diastereoselective in the Michael addition to 5-, 6-, and 7-ring enones. With the enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides, high regio- and diastereoselectivities (88-90% diastereomeric excess) have been achieved in the Michael addition reaction of one of the diastereomers (cis series). The Michael reaction of the anions derived from the trans series were not diastereoselective (similar to 10% diastereomeric excess). The origin of the addition selectivity can be rationalized by (1) consideration of the structure and conformational preferences of the allyl anion (parallel conformation, s-trans, no lithium contact), (2) conformational analysis of the 1,3,2-oxazaphosphorinane 2-oxide ring (chair, equatorial allyl group) and (3) assumption of a 10-membered ring transition state structure with lithium coordination of the enone.

  DOI：

  10.1021/jo00128a028
• 作为产物：
  描述：

  (S)-4-N-tert-butylamino-2-butanol 在 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 10.0h， 生成 (S)-(2u,6l)-3-(1,1-Dimethylethyl)-6-methyl-2-(2-propenyl)-1,3,2-oxazaphosphorinane 2-oxide
  参考文献：
  名称：

  Asymmetric Michael Addition Reaction of Phosphorus-Stabilized Allyl Anions with Cyclic Enones

  摘要：

  The asymmetric Michael addition reaction of chirally modified P-allyl anions derived from enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides has been investigated with cyclic enones. The racemic 1,3,2-oxazaphosphorinane 2-oxide 3 has been shown to be extremely diastereoselective in the Michael addition to 5-, 6-, and 7-ring enones. With the enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides, high regio- and diastereoselectivities (88-90% diastereomeric excess) have been achieved in the Michael addition reaction of one of the diastereomers (cis series). The Michael reaction of the anions derived from the trans series were not diastereoselective (similar to 10% diastereomeric excess). The origin of the addition selectivity can be rationalized by (1) consideration of the structure and conformational preferences of the allyl anion (parallel conformation, s-trans, no lithium contact), (2) conformational analysis of the 1,3,2-oxazaphosphorinane 2-oxide ring (chair, equatorial allyl group) and (3) assumption of a 10-membered ring transition state structure with lithium coordination of the enone.

  DOI：

  10.1021/jo00128a028

文献信息

• Asymmetric Michael Addition Reaction of Phosphorus-Stabilized Allyl Anions with Cyclic Enones
  作者：Scott E. Denmark、Jung-Ho Kim

  DOI：10.1021/jo00128a028

  日期：1995.11

  The asymmetric Michael addition reaction of chirally modified P-allyl anions derived from enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides has been investigated with cyclic enones. The racemic 1,3,2-oxazaphosphorinane 2-oxide 3 has been shown to be extremely diastereoselective in the Michael addition to 5-, 6-, and 7-ring enones. With the enantiomerically enriched 2-allyl-1,3,2-oxazaphosphorinane 2-oxides, high regio- and diastereoselectivities (88-90% diastereomeric excess) have been achieved in the Michael addition reaction of one of the diastereomers (cis series). The Michael reaction of the anions derived from the trans series were not diastereoselective (similar to 10% diastereomeric excess). The origin of the addition selectivity can be rationalized by (1) consideration of the structure and conformational preferences of the allyl anion (parallel conformation, s-trans, no lithium contact), (2) conformational analysis of the 1,3,2-oxazaphosphorinane 2-oxide ring (chair, equatorial allyl group) and (3) assumption of a 10-membered ring transition state structure with lithium coordination of the enone.