(t-Bu-NH)P(μ-N-t-Bu)2P(NH-t-Bu)=C(CO2Me)CH2(CO2Me) | 1313588-57-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (t-Bu-NH)P(μ-N-t-Bu)2P(NH-t-Bu)=C(CO2Me)CH2(CO2Me)
• 英文别名: Dimethyl 2-[1,3-ditert-butyl-2,4-bis(tert-butylamino)-1,3,2lambda5,4-diazadiphosphetidin-2-ylidene]butanedioate；dimethyl 2-[1,3-ditert-butyl-2,4-bis(tert-butylamino)-1,3,2λ5,4-diazadiphosphetidin-2-ylidene]butanedioate
• CAS: 1313588-57-6
• 化学式: C₂₂H₄₆N₄O₄P₂
• 分子量: 492.579
• InChiKey: ZPQBIDSFCCYWEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  32
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  83.1
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  cis-[tBu(H)NP(μ-NtBu)]2 、 马来酸二甲酯 以 甲苯 为溶剂， 反应 72.0h， 以90%的产率得到(t-Bu-NH)P(μ-N-t-Bu)2P(NH-t-Bu)=C(CO2Me)CH2(CO2Me)
  参考文献：
  名称：

  Cyclodiphosph(III)azane chemistry – Ylides from the reaction of [(RNH)P-N(t-Bu)]2 [R=t-Bu, i-Pr] with dimethyl maleate and chiral ansa-type derivatives from reaction of [ClP-N(t-Bu)]2 with a substituted BINOL

  摘要：

  Use of a simple inorganic ring system with the cyclodiphosph(III) azane skeleton [e.g. [(RNH)P-N(t-Bu)](2) [R = t-Bu (7), i-Pr (8)] to probe some of the intermediates proposed in phosphine mediated organic reactions is highlighted. Thus the reaction of 7-8 with the allenylphosphine oxide Ph2P(O)C(Ph)=C=CH2 (9) affords the phosphinimines [(RNH)P(mu-N-t-Bu)(2)P(=N-R)-C(=CH2) CH(Ph)-P(O)Ph-2] [R= t-Bu (10), i-Pr (11)], while a similar reaction of 7-8 with dimethyl maleate (or dimethyl fumarate) affords the ylides [(RNH) P(mu-N-t-Bu)(2)P(NH-R)=C(CO2Me)-CH2(CO2Me) [R = t-Bu (18), i-Pr (19)]. The implication of such reactions on phosphine mediated organic transformations including Morita-Baylis-Hillman reaction is mentioned. In a rather rare type of situation, an unusually long phosphoryl (P=O) bond [1.538 (5) angstrom] as revealed the X-ray structure of {(R)-6,6'-(t-Bu)(2)-1,1'-(C10H5)(2)-2,2'-O-2-}{P(O)(N-t-Bu)(2)-P(Se)} (27) is rationalized by means of crystallographic disorder in packing after comparing the data with that in the literature and {1,1'-(C10H6)(2)-2,2'-O-2}{P(Se)(N-t-Bu)(2)-P(Se)} (29). X-ray structures of the new compounds 10-11, 18-19, 27 and 29 are discussed. Compound 10 crystallizes in the chiral space group Pca2(1) with (S)-chirality at the carbon center [-C(=CH2) CH(Ph)-P] suggesting a case of spontaneous resolution through crystallization. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.12.072

文献信息

• Cyclodiphosph(III)azane chemistry – Ylides from the reaction of [(RNH)P-N(t-Bu)]2 [R=t-Bu, i-Pr] with dimethyl maleate and chiral ansa-type derivatives from reaction of [ClP-N(t-Bu)]2 with a substituted BINOL
  作者：K.C. Kumara Swamy、G. Gangadhararao、Venu Srinivas、N.N. Bhuvan Kumar、E. Balaraman、Manab Chakravarty

  DOI：10.1016/j.ica.2010.12.072

  日期：2011.6

  Use of a simple inorganic ring system with the cyclodiphosph(III) azane skeleton [e.g. [(RNH)P-N(t-Bu)](2) [R = t-Bu (7), i-Pr (8)] to probe some of the intermediates proposed in phosphine mediated organic reactions is highlighted. Thus the reaction of 7-8 with the allenylphosphine oxide Ph2P(O)C(Ph)=C=CH2 (9) affords the phosphinimines [(RNH)P(mu-N-t-Bu)(2)P(=N-R)-C(=CH2) CH(Ph)-P(O)Ph-2] [R= t-Bu (10), i-Pr (11)], while a similar reaction of 7-8 with dimethyl maleate (or dimethyl fumarate) affords the ylides [(RNH) P(mu-N-t-Bu)(2)P(NH-R)=C(CO2Me)-CH2(CO2Me) [R = t-Bu (18), i-Pr (19)]. The implication of such reactions on phosphine mediated organic transformations including Morita-Baylis-Hillman reaction is mentioned. In a rather rare type of situation, an unusually long phosphoryl (P=O) bond [1.538 (5) angstrom] as revealed the X-ray structure of (R)-6,6'-(t-Bu)(2)-1,1'-(C10H5)(2)-2,2'-O-2-}P(O)(N-t-Bu)(2)-P(Se)} (27) is rationalized by means of crystallographic disorder in packing after comparing the data with that in the literature and 1,1'-(C10H6)(2)-2,2'-O-2}P(Se)(N-t-Bu)(2)-P(Se)} (29). X-ray structures of the new compounds 10-11, 18-19, 27 and 29 are discussed. Compound 10 crystallizes in the chiral space group Pca2(1) with (S)-chirality at the carbon center [-C(=CH2) CH(Ph)-P] suggesting a case of spontaneous resolution through crystallization. (C) 2011 Elsevier B.V. All rights reserved.