(3aR,7aR)-2-crotyloctahydro-1H-1,3-dimethyl-1,3,2-benzadiazaphosphole 2-oxide | 150932-41-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: (3aR,7aR)-2-crotyloctahydro-1H-1,3-dimethyl-1,3,2-benzadiazaphosphole 2-oxide
• 英文别名: (3aR,7aR)-2-[(E)-but-2-enyl]-1,3-dimethyl-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
• CAS: 150932-41-5
• 化学式: C₁₂H₂₃N₂OP
• 分子量: 242.301
• InChiKey: UHAPIICFZFIGMI-GKUNOOHESA-N

物化性质

• 沸点：
  326.0±35.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aR,7aR)-2-crotyloctahydro-1H-1,3-dimethyl-1,3,2-benzadiazaphosphole 2-oxide 在 吡啶 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 生成 (2R,3S)-2-[(E)-(1S,2R)-4-((3aR,7aR)-1,3-Dimethyl-2-oxo-octahydro-2λ⁵-benzo[1,3,2]diazaphosphol-2-yl)-2-methyl-1-phenyl-but-3-enyl]-4-methyl-3-phenyl-pentanedioic acid 1-tert-butyl ester 5-isopropyl ester
  参考文献：
  名称：

  Highly stereocontrolled sequential asymmetric Michael addition reactions with cinnamate esters - generation of three and four contiguous stereogenic centers on seven-carbon acyclic motifs

  摘要：

  The reaction of allyl and crotyl bicyclic chiral phosphonamide anions with two cinnamate esters leads to a sequential Michael reaction with excellent diastereoselectivity. The option to quench enolates with methyl iodide greatly enhances the versatility of the reaction in the synthesis of acyclic seven-carbon chains with vicinal and alternating C-methyl and C-phenyl substituents.

  DOI：

  10.1016/s0040-4039(00)78330-4
• 作为产物：
  描述：

  (1R,2R)-(-)-N,N'-二甲基-1,2-环己二胺 、 crotylphosphonic dichloride 在 三乙胺 作用下， 以 苯 为溶剂， 反应 18.0h， 以93%的产率得到(3aR,7aR)-2-crotyloctahydro-1H-1,3-dimethyl-1,3,2-benzadiazaphosphole 2-oxide
  参考文献：
  名称：

  手性膦酰胺阴离子向α，β-不饱和羰基化合物的不对称共轭加成。一种通用的方法来取代毒substituted

  摘要：

  衍生自手性非外消旋烯丙基，巴豆基和肉桂基双环C（2）对称膦酰胺的阴离子与α，β-不饱和环酮，酯，内酯和内酰胺的反应在试剂的γ位发生。产物是非对映体纯的或富集的β-取代的羰基化合物。该方法还可以轻松地以一锅序列的方式多达三个立体定位中心的邻近取代，在某些情况下还包括季碳原子。

  DOI：

  10.1021/jo000388g

文献信息

• Asymmetric conjugate additions of chiral allyl- and crotylphosphonamide anions to .alpha.,.beta.-unsaturated carbonyl compounds: highly stereocontrolled access to vicinally substituted carbon centers and chemically asymmetrized chirons
  作者：Stephen Hanessian、Arthur Gomtsyan、Andrew Payne、Yolande Herve、Serge Beaudoin

  DOI：10.1021/jo00071a004

  日期：1993.9

  Reactions of anions derived from chiral nonracemic allyl and crotyl bicyclic phosphonamides with alpha,beta-unsaturated cyclic ketones, esters, lactones, and lactams take place at the gamma-position of the reagents and lead to diastereomerically pure or highly enriched products of conjugate addition. The option to quench the corresponding enolates with various alkyl halides offers a versatile approach to vicinal substitution including the generation of quaternary carbon centers.
• Synthesis and Stereochemical Confirmation of the Secoiridoid Glucosides Nudiflosides D and A
  作者：Stephen Hanessian、Emily Mainetti、Fabien Lecomte

  DOI：10.1021/ol0615230

  日期：2006.8.1

  We describe herein an efficient access to the highly substituted cyclopentane unit present in the Nudifloside secoiridoid family via crotyl phosphonamide anion mediated conjugate addition to cyclopentenone.
• Asymmetric Conjugate Additions of Chiral Phosphonamide Anions to α,β-Unsaturated Carbonyl Compounds. A Versatile Method for Vicinally Substituted Chirons
  作者：Stephen Hanessian、Arthur Gomtsyan、Nadia Malek

  DOI：10.1021/jo000388g

  日期：2000.9.1

  Reactions of anions derived from chiral nonracemic allyl, crotyl, and cinnamyl bicyclic C(2)-symmetrical phosphonamides with alpha, beta-unsaturated cyclic ketones, esters, lactones, and lactams take place at the gamma-position of the reagents. The products are diastereomerically pure or enriched beta-substituted carbonyl compounds. The method also provides easy access to vicinal substitution of as

  衍生自手性非外消旋烯丙基，巴豆基和肉桂基双环C（2）对称膦酰胺的阴离子与α，β-不饱和环酮，酯，内酯和内酰胺的反应在试剂的γ位发生。产物是非对映体纯的或富集的β-取代的羰基化合物。该方法还可以轻松地以一锅序列的方式多达三个立体定位中心的邻近取代，在某些情况下还包括季碳原子。
• Highly stereocontrolled sequential asymmetric Michael addition reactions with cinnamate esters - generation of three and four contiguous stereogenic centers on seven-carbon acyclic motifs
  作者：Stephen Hanessian、Arthur Gomtsyan

  DOI：10.1016/s0040-4039(00)78330-4

  日期：1994.10

  The reaction of allyl and crotyl bicyclic chiral phosphonamide anions with two cinnamate esters leads to a sequential Michael reaction with excellent diastereoselectivity. The option to quench enolates with methyl iodide greatly enhances the versatility of the reaction in the synthesis of acyclic seven-carbon chains with vicinal and alternating C-methyl and C-phenyl substituents.