deutero 2-(diphenylphosphino)benzaldehyde | 1394246-13-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: deutero 2-(diphenylphosphino)benzaldehyde
• CAS: 1394246-13-9
• 化学式: C₁₉H₁₅OP
• 分子量: 291.293
• InChiKey: DRCPJRZHAJMWOU-RWFJLFJASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.26
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  deutero 2-(diphenylphosphino)benzaldehyde 、 (2-溴苯基)二苯基膦 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 0.5h， 以20%的产率得到
  参考文献：
  名称：

  通过铑α-羟烷基烷基络合物的聚合（De）加氢途径

  摘要：

  We report the convergent reaction pathways between [RhH(PPh3)4] and POP ketone (1) and alcohol (2) ligands that terminate in the formation of an alpha-hydroxylalkyl rhodium(I) complex (3), representing two halves of a formal reduction/oxidation pathway between 1 and 2. In the case of hydride transfer to 1, the formation of the a-hydroxylalkyl rhodium(I) complex (3) proceeds via a rare hydrido(eta(2)-carbonyl) complex (4). CH activation in 2 at the proligands central methine position, rather than OH activation of the hydroxy motif, followed by loss of dihydrogen also generates the alpha-hydroxylalkyl rhodium(I) complex (3). The validity of the postulated reaction pathways is probed with DFT calculations. The observed reactivity supports a-hydroxylalkyl complexes as competent intermediates in ketone hydrogenation catalyzed by rhodium hydrides and suggest that ligands 1 and 2 may be noninnocent coligands in reported hydrogenation catalyst systems in which they are utilized.

  DOI：

  10.1021/acs.organomet.7b00158
• 作为产物：
  描述：

  N,N-二甲基甲酰胺-d7 、 (2-溴苯基)二苯基膦 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 0.5h， 以52%的产率得到deutero 2-(diphenylphosphino)benzaldehyde
  参考文献：
  名称：

  通过铑α-羟烷基烷基络合物的聚合（De）加氢途径

  摘要：

  We report the convergent reaction pathways between [RhH(PPh3)4] and POP ketone (1) and alcohol (2) ligands that terminate in the formation of an alpha-hydroxylalkyl rhodium(I) complex (3), representing two halves of a formal reduction/oxidation pathway between 1 and 2. In the case of hydride transfer to 1, the formation of the a-hydroxylalkyl rhodium(I) complex (3) proceeds via a rare hydrido(eta(2)-carbonyl) complex (4). CH activation in 2 at the proligands central methine position, rather than OH activation of the hydroxy motif, followed by loss of dihydrogen also generates the alpha-hydroxylalkyl rhodium(I) complex (3). The validity of the postulated reaction pathways is probed with DFT calculations. The observed reactivity supports a-hydroxylalkyl complexes as competent intermediates in ketone hydrogenation catalyzed by rhodium hydrides and suggest that ligands 1 and 2 may be noninnocent coligands in reported hydrogenation catalyst systems in which they are utilized.

  DOI：

  10.1021/acs.organomet.7b00158

文献信息

• <i>C</i>₂-Symmetric Iron(II) Diphosphine–Dialkoxide Dicarbonyl and Related Complexes
  作者：Hao Lei、Aaron M. Royer、Thomas B. Rauchfuss、Danielle Gray

  DOI：10.1021/om300631a

  日期：2012.9.10

  adduct Fe(PCHO)(CO)4 (2), which was obtained by addition of PCHO to Fe2(CO)9. Compound 2 decarbonylates to give tricarbonyl Fe(κ1,η2-PCHO)(CO)3 (3), which features a π-bonded aldehyde. Photolysis of 2 gives a mixture of 3 and isomeric hydride HFe(κ2-PCO)(CO)3. Complex 3 reacts with an additional equivalent of PCHO to afford 1, whereas treatment with PPh3 afforded the substituted product Fe(κ1,η2-PCHO)(PPh3)(CO)2

  Fe（bda）（CO）3（bda =苄叉基丙酮）与Ph 2 P-2-C 6 H 4 CHO（PCHO）反应，制得双膦双醇盐配合物Fe [（Ph 2 PC 6 H 4）2 C 2 H 2 O 2 ]（CO）2（1）由两个甲酰基与Fe（0）氧化为Fe（II）的头对头偶联而产生。晶体学研究表明1具有反式转化为CO的顺式烷氧基配体。两个膦基是相互反式的P–Fe–P角度为167.44（4）°。从加合物Fe（PCHO）（CO）4（2）开始检查通向1的途径，该加合物是通过将PCHO加到Fe 2（CO）9中获得的。化合物2 decarbonylates，得到三羰基铁（κ 1，η 2 -PCHO）（CO）3（3），其特点是π键合的醛。的光解2给出的混合物3和异构体氢化HFE（κ 2 -PCO）（CO）3。配合物3与另外等价的PCHO反应生成1，而用PPH治疗3，得到取代产物的Fe（κ 1，η 2 -PCHO）（PPH