(3aR,7aR)-2,3,3a,4,5,6,7,7a-Octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,2,3-benzodiazaphosphole-2-oxide | 138421-32-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环化合物
• 英文名称: (3aR,7aR)-2,3,3a,4,5,6,7,7a-Octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,2,3-benzodiazaphosphole-2-oxide
• 英文别名: (3aR,7aR)-1,3-dineopentyloctahydro-1H-benzo[d][1,3,2]diazaphosphole 2-oxide；(3aR,7aR)-1,3-bis(2,2-dimethylpropyl)-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
• CAS: 138421-32-6
• 化学式: C₁₆H₃₃N₂OP
• 分子量: 300.425
• InChiKey: FKNQBZVZUVPLCE-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 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)-2,3,3a,4,5,6,7,7a-Octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,2,3-benzodiazaphosphole-2-oxide 在 正丁基锂 、 potassium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 13.0h， 生成
  参考文献：
  名称：

  具有手性二氮杂膦基团的新型磺鎓叶立德作为不对称环丙烷化试剂的合成

  摘要：

  由手性 N,N'-取代（苄基、异丙基、新戊基）膦酰胺衍生的锍叶立德是通过将适当的手性亚磷酸二酰胺与氢化钾和氯甲基甲基硫醚反应制备的，然后在 AgBF4 存在下与甲基碘反应得到相应的锍盐高产量。其中之一通过 X 射线晶体学进行了分析。用不同碱（二异丙基胺锂、锂、碳酸钾）处理后的盐被原位转化为叶立德，叶立德与活化的烯烃反应生成膦酰基环丙烷，作为两种非对映异构体的混合物，具有中等至高的非对映选择性。

  DOI：

  10.1002/hc.21183
• 作为产物：
  描述：

  (1R,2R)-N,N'-bis(2,2-dimethylpropyl)-1,2-cyclohexanediamine 在 水 、 三乙胺 、 三氯化磷 作用下， 以 甲苯 为溶剂， 生成 (3aR,7aR)-2,3,3a,4,5,6,7,7a-Octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,2,3-benzodiazaphosphole-2-oxide
  参考文献：
  名称：

  手性亚磷酸二酰胺的制备与反应

  摘要：

  通过将N，N'-二取代的C 2二胺与PCl 3缩合，然后再加入等价的水来制备手性亚磷酸二酰胺。这些酸用正丁基锂或LDA脱质子化得到的锂盐与烷基卤化物平稳反应，以高收率得到取代的膦酰胺。

  DOI：

  10.1016/0040-4039(91)80151-u
• 作为试剂：
  描述：

  苯并咪唑 、 3,4-二甲基碘苯 在 bis(1,5-cyclooctadiene)nickel (0) 、 三甲基铝 、 铜 、 caesium carbonate 、 (3aR,7aR)-2,3,3a,4,5,6,7,7a-Octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,2,3-benzodiazaphosphole-2-oxide 作用下， 以 正己烷 、 甲苯 、 乙腈 为溶剂， 反应 12.0h， 生成 5,6-dibutyl-2,3-dimethylbenzo[4,5]imidazo[1,2-a]quinolone
  参考文献：
  名称：

  Ni-Catalyzed Dual C–H Annulation of Benzimidazoles with Alkynes for Synthesis of π-Extended Heteroarenes

  摘要：

  DOI：

  10.1021/acs.orglett.1c01253

文献信息

• Koeller, Kevin J.; Rath, Nigam P.; Spilling, Christopher D., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 103, # 1-4, p. 171 - 182
  作者：Koeller, Kevin J.、Rath, Nigam P.、Spilling, Christopher D.

  DOI：——

  日期：——
• The synthesis, structure and properties of diazaphospholes: Reagents and ligands for asymmetric synthesis
  作者：Antonette De la Cruz、Kevin J Koeller、Nigam P Rath、Christopher D Spilling、Isabel C.F Vasconcelos

  DOI：10.1016/s0040-4020(98)00502-x

  日期：1998.8

  Reaction of C-2 diamines with PCl3 and Et3N in toluene, followed by water or hydrogen sulfide, gave a series of cyclic phosphorous acid diamides (diazaphosphole oxides) and thiophosphorous acid diamides (diazaphosphole sulfides), respectively. Similarly, reaction of diamines with phenyl dichlorophosphine gave phenyl diazaphospholes. The synthesis, properties, and structure of these diazaphospholes are reported. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthesis of Nonracemic Dimethyl α-(Hydroxyfarnesyl)phosphonates via Oxidation of Dimethyl Farnesylphosphonate with (Camphorsulfonyl)oxaziridines
  作者：Diana M. Cermak、Yanming Du、David F. Wiemer

  DOI：10.1021/jo980984z

  日期：1999.1.1

  Several strategies for synthesis of nonracemic dimethyl alpha-(hydroxyfarnesyl)phosphonate and the parent phosphonic acid have been explored. Separation of diastereomeric derivatives prepared by esterification of racemic a-hydroxy phosphonate with (S)-(+)-O-methylmandelic acid was possible, and these diastereomers could be assigned absolute stereochemistry on the basis of literature precedent; However, hydrolysis to the alpha-hydroxy phosphonic acid was accompanied by extensive isomerization. Addition of a nonracemic phosphonamidite to farnesal also gave nonracemic material, but again hydrolysis was problematic. Oxidation of dimethyl farnesylphosphonate anion with nonracemic (camphorsulfonyl)oxaziridines was shown to be regio- and stereoselective for formation of the a-hydroxy phosphonate. Enantiomeric excess of similar to 70% ee was established by conversion of the oxidation products to their (S)-(+)-O-methylmandelate derivatives. Although hydrolysis of these methyl esters was accompanied by extensive racemization, both enantiomers of alpha-(hydroxyfarnesyl)phosphonic acid were obtained in low ee by this strategy.
• Reactions of Chiral Phosphorous Acid Diamides: The Asymmetric Synthesis of Chiral .alpha.-Hydroxy Phosphonamides, Phosphonates, and Phosphonic Acids
  作者：Vincent J. Blazis、Kevin J. Koeller、Christopher D. Spilling

  DOI：10.1021/jo00109a025

  日期：1995.2

  Addition of aldehydes to the anions of chiral phosphorous acid diamides in THF solution gave a-hydroxy phosphonamides in good yield. The diastereoselectivity was strongly dependent upon the diamide used and ranged from poor to good. The phosphorous acid diamides 2a and 2b (R(1) = -(CH2)4-,R(2) = CH(2)Ph and CH(2)CMe(3), respectively) gave the best selectivity, and their reactions with a range of aldehydes were studied. Diamide 2b consistently gave good selectivities, whereas diamide 2a was only moderately selective. Aromatic, aliphatic, and unsaturated aldehydes are tolerated under the reaction conditions. The phosphonamides were hydrolyzed with aqueous HCl in dioxane to give a-hydroxy phosphonic acids. While direct methanolysis of the phosphonamides was unsuccessful, methylation of the phosphonic acids with diazomethane gave alpha-hydroxy dimethylphosphonates.
• Blazis, Vincent; Cruz, Antonette De La; Koeller, Kevin, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 75, # 1-4, p. 159 - 162
  作者：Blazis, Vincent、Cruz, Antonette De La、Koeller, Kevin、Spilling, Christopher D.

  DOI：——

  日期：——