(R)-3-(dimethyl(phenyl)silyl)-1,3-diphenylpropan-1-one | 156204-22-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (R)-3-(dimethyl(phenyl)silyl)-1,3-diphenylpropan-1-one
• 英文别名: (3R)-3-[dimethyl(phenyl)silyl]-1,3-diphenylpropan-1-one
• CAS: 156204-22-7
• 化学式: C₂₃H₂₄OSi
• 分子量: 344.528
• InChiKey: BAGFORDIVMFSTQ-HSZRJFAPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  在 硫酸 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以91%的产率得到(R)-3-(dimethyl(phenyl)silyl)-1,3-diphenylpropan-1-one
  参考文献：
  名称：

  铜催化α，β-不饱和酮亚胺的立体和对映选择性1,4-甲硅烷化合成功能化的烯丙基硅烷

  摘要：

  已经开发了铜催化的α，β-不饱和磺酰基酮亚胺的共轭硅烷基化反应。通过调节反应中使用的配体，分别以高收率获得相应的E-和Z-立体选择性官能化的烯丙基硅烷产物。此外，在手性Pybox配体的存在下也获得了高对映选择性（E）-β-甲苯磺酰基取代的烯丙基硅烷。并且相应的产品可以轻松转换为其他有用的合成子。

  DOI：

  10.1021/acscatal.8b01547

文献信息

• Rhodium(I)-catalyzed enantioselective 1,4-addition of nucleophilic silicon
  作者：Christian Walter、Roland Fröhlich、Martin Oestreich

  DOI：10.1016/j.tet.2009.01.111

  日期：2009.7

  rhodium(I) by means of an RhI–OH complex, enables the conjugate transfer of nucleophilic silicon onto α,β-unsaturated acceptors. Pre- or in situ formed cationic rhodium(I)–binap complexes catalyze this novel carbon–silicon bond formation with exceptional enantiocontrol, 92 to >99% ee for cyclic carbonyl and carboxyl compounds as well as >99% ee for acyclic carboxyl compounds.

  铑（I）催化的硅-硼键活化，即通过Rh I -OH络合物将硅从硼转变为铑（I），可以将亲核硅共轭转移到α，β上-不饱和受体。预制的或原位形成的阳离子铑（I）-联萘酚配合物可催化这种新型的碳-硅键形成，具有出色的对映体控制能力，环状羰基和羧基化合物的ee为92％至> 99％ee，无环羧基化合物的ee> 99％。
• An Insoluble Copper(II) Acetylacetonate–Chiral Bipyridine Complex that Catalyzes Asymmetric Silyl Conjugate Addition in Water
  作者：Taku Kitanosono、Lei Zhu、Chang Liu、Pengyu Xu、Shu̅ Kobayashi

  DOI：10.1021/jacs.5b11418

  日期：2015.12.16

  Acicular purplish crystals were obtained from Cu(acac)(2) and a chiral bipyridine ligand. Although the crystals were not soluble, they nevertheless catalyzed asymmetric silyl conjugate addition of lip ophilic substrates in water. Indeed, the reactions proceeded efficiently only in water; they did not proceed well either in organic solvents or in mixed water/organic solvents in which the catalyst/substrates were soluble. This is in pronounced contrast to conventional organic reactions wherein the catalyst/substrates tend to be in solution. Several advantages of the chiral Cu(II) catalysis in water over previously reported catalyst systems have been demonstrated. Water is expected to play a prominent role in constructing and stabilizing sterically confined transition states and accelerating subsequent protonation to achieve high yields and enantioselectivities.