[Phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane | 897384-93-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane
• CAS: 897384-93-9；1000592-00-6；897385-00-1
• 化学式: C₂₁H₂₀NP
• 分子量: 317.37
• InChiKey: NKTJSJBIPWTKGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 [Phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane 以 二氯甲烷 为溶剂， 以53%的产率得到Dichloropalladium;[phenyl(pyridin-2-yl)methylidene]-(2,4,6-trimethylphenyl)phosphane
  参考文献：
  名称：

  P,N-Chelate Complexes of Pd(II) and Pt(II) Based on a Phosphaalkene Motif:  A Catalyst for the Overman−Claisen Rearrangement

  摘要：

  The reaction of E/Z-MesP=C(Ph)(Py) (1, Mes = 2,4,6-Me(3)C(6)H(2)-) with (cod)PtCl(2) or (cod)PdCl(2) affords P,N-chelate complexes [MesP C(Ph)(Py)PtCl(2)] (2a) and [MesP=C(Ph)(Py)PdCl(2)] (2b), respectively. Compounds 2a and 2b were fully characterized spectroscopically, and both were characterized by X-ray crystallography. The molecular structures exhibited almost identical metrical parameters. The P=C bond lengths in 2a and 2b [1.672(4) and 1.675(3) A, respectively] were shortened substantially with respect to that of 1 [1.7043(16) A]. Complex 2b was explored as a catalyst for the Overman-Claisen rearrangement. Several allyl trichloroacetimidate substrates [HN=C(CCl(3))OCH(2)CH=CHR(1): 3a, R(1) = Me; 3b, R(1) = n-Pr; 3c, R(1) = n-Hep; 3d, R(1) = CH(2)CH(2)Ph; 3e, R(1) = i-Pr] were successfully rearranged to their respective branched amides [H(2)C=CHCH(R(1))NHC(O)CCl(3): 4a-e] using 5 mol % 2b as catalyst. Isolated yields ranged from a low of 33% for the bulky 4e to a high of 91% for 4a.

  DOI：

  10.1021/om700784x

文献信息

• 4-Phosphino-Substituted N-Heterocyclic Carbenes (NHCs) from the Abnormal Reaction of NHCs with Phosphaalkenes
  作者：Joshua I. Bates、Derek P. Gates

  DOI：10.1021/om3003174

  日期：2012.6.25

  The activation of the P═C bond of phosphaalkenes with N-heterocyclic carbenes (NHCs) offers a convenient means to introduce new functionality at the 4-position of an NHC. Treatment of MesP═CRR′ (2a: R = R′ = Ph; 2b: R = Ph, R′ = 2-C5H4N; 2c: R = R′ = 4-C6H4F) with 1,3-dimesitylimidazol-2-ylidene [:C(NMesCH)2, IMes, Mes = 2,4,6-Me3C6H2] affords 4-phosphino-2-carbenes :C(NMes)2CHC(PMesCHRR′)NMes [1a:

  磷烯烃与N-杂环卡宾（NHC）的P═C键的活化为在NHC的4位引入新的功能性提供了方便的方法。用1处理MesP═CRR'（2a：R = R'= Ph; 2b：R = Ph，R'= 2-C 5 H 4 N; 2c：R = R'= 4-C 6 H 4 F） ，3-dimesitylimidazol-2-ylidene [：C（NMesCH）2，IMes，Mes = 2,4,6-Me 3 C 6 H 2 ]得到4-膦基-2-卡宾：C（NMes）2 CHC（PMesCHRR '）NMes [ 1a：R = R'= Ph; 1b：R = Ph，R'= 2-C 5H 4 N；1c：R ＝ R′＝ 4-C 6 H 4 F]。显着地，这些官能NHC保留了母卡宾官能团，并且另外包含膦部分。报道了配合物[（1a）M（cod）Cl]（4）和顺式-[（1a）M（CO）2 Cl]（5）（M = Ir，Rh）的制备和光谱表征。平均CO伸缩频率（ν