tert-butyldiphenyl(phenylselanyl)silane | 76358-44-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tert-butyldiphenyl(phenylselanyl)silane
• 英文别名: Tert-butyl-diphenyl-phenylselanylsilane
• CAS: 76358-44-6
• 化学式: C₂₂H₂₄SeSi
• 分子量: 395.478
• InChiKey: KDRYWUBGSWBOEQ-UHFFFAOYSA-N

物化性质

• 熔点：
  57 °C
• 沸点：
  438.0±18.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.58
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tert-butyldiphenyl(phenylselanyl)silane 在 碘 作用下， 生成 叔丁基二苯基甲氧基硅烷
  参考文献：
  名称：

  Silyl halides from (phenylseleno)silanes. Reaction with oxiranes and alcohols to give hydrolytically stable silyl ethers

  摘要：

  DOI：

  10.1021/jo00320a012
• 作为产物：
  描述：

  triethylsilyl phenylselenide 在 sodium 、 氯 作用下， 以 四氯化碳 为溶剂， 反应 23.0h， 生成 tert-butyldiphenyl(phenylselanyl)silane
  参考文献：
  名称：

  Silyl halides from (phenylseleno)silanes. Reaction with oxiranes and alcohols to give hydrolytically stable silyl ethers

  摘要：

  DOI：

  10.1021/jo00320a012
• 作为试剂：
  描述：

  ethyl 2-(phenylselanyl)acetate 、 4-tert-butyldimethylsilyloxy-1-decene 在 tert-butyldiphenyl(phenylselanyl)silane 9,10-二甲氧基蒽 、 氧气 、 维生素 C 作用下， 以 乙腈 为溶剂， 以61%的产率得到6-(tert-Butyl-dimethyl-silanyloxy)-4-phenylselanyl-dodecanoic acid ethyl ester
  参考文献：
  名称：

  PhSeSiR₃-Catalyzed Group Transfer Radical Reactions

  摘要：

  A novel design for initiating radical-based chemistry in a catalytic fashion is described. The design of the concept is based on the phenylselenyl group transfer reaction from alkyl phenyl selenides by utilizing PhSeSiR3 (1) as a catalytic reagent. The reaction is initiated by the homolytic cleavage of -C-Se- bond of an alkyl phenyl selenide by the in situ generated alkylsilyl radical (R3Si.), obtained by the mesolysis of PhSeSiR3](.-) (1(.-)). The oxidative dimerization of counteranion PhSe- to PhSeSePh functions as radical terminator. The generation of 1(.-) is achieved by the photoinduced electron transfer (PET) promoted reductive activation of 1 through a photosystem comprising of a visible-light (410 nm)-absorbing electron rich DMA as an electron donor and ascorbic acid as a co-oxidant (Figure 1). The optimum mole ratio between the catalyst 1 and alkyl phenyl selenides for successful reaction is established to be 1:10. The generality of the concept is demonstrated by carrying out variety of radical reactions such as cyclization (10, 15-18), intermolecular addition (25), and tandem annulations (32).

  DOI：

  10.1021/jo000128z

文献信息

• <i>p</i>-Silylation of Arenes via Organic Photoredox Catalysis: Use of <i>p</i>-Silylated Arenes for Exclusive <i>o</i>-Silylation, <i>o</i>-Acylation, and <i>o</i>-Alkylation Reactions
  作者：Ganesh Pandey、Sandip Kumar Tiwari、Pushpendra Singh、Pradip Kumar Mondal

  DOI：10.1021/acs.orglett.1c02672

  日期：2021.10.15

  Photocatalytic regiospecific p-silylation of arenes has been achieved by the coupling of in situ generated silyl radical with arene radical cation. The strategy involves reductive activation of PhSe–SiR3 and single electron transfer from the electron rich arene to 9,10-dimethoxyanthracene radical cation (DMA•+). p-Silyl arenes, thus formed, are further utilized for exclusive o-silylation reaction and

  通过将原位生成的甲硅烷基自由基与芳烃自由基阳离子偶联，已经实现了芳烃的光催化区域特异性p-甲硅烷基化。该策略包括 PhSe-SiR 3 的还原活化和从富电子芳烃到 9,10-二甲氧基蒽自由基阳离子 (DMA •+ ) 的单电子转移。如此形成的对-甲硅烷基芳烃进一步用于排他性的o-甲硅烷基化反应和区域特异性的o-酰化以及o-烷基化反应。
• Generation and Mesolysis of PhSeSiR₃]^•-:  Mechanistic Studies by Laser Flash Photolysis and Application for Bimolecular Group Transfer Radical Reactions
  作者：Ganesh Pandey、K. S. Sesha Poleswara Rao、D. K. Palit、J. P. Mittal

  DOI：10.1021/jo972345e

  日期：1998.6.1

  The investigation presented in this paper explores the mechanistic aspects and synthetic potentials of PET promoted reductive activation of selenosilane la to its radical anion la(-.). PET activation of la is achieved through a photosystem comprising a light-absorbing electron-rich aromatic (ERA), such as DMN or DMA, as an electron donor and ascorbic acid as a co-oxidant. The evidence for the ET from excited singlet states of DMN as well as DMA to la is suggested by estimating negative Delta G(et) (-51 and -43.46 kcal mol(-1), respectively) values and nearly diffusion-controlled fluorescence quenching rate constants (k(q)TR) 0.36 x 10(10) M-1 s(-1) and 0.28 x 10(10) M-1 s(-1), respectively, from time-resolved fluorescence quenching study. The transient absorption spectra of DMN.+, DMA(.+), and la(.-) are obtained initially by pulse radiolysis in order to correlate the time-resolved absorption spectral data. Laser flash photolysis studies in the nanosecond time domain have confirmed the generation of la(.-), DMN.+, and DMA(.+), supporting the participation of the triplet state of DMN or DMA in the ET reaction. Mesolytic cleavage of 1a(.-) produced a silyl radical and a phenyl selenide anion. The preparative PET activation of la in acetonitrile in the presence of DMN or DMA leads to the formation of 5 and 6, confirming the fragmentation pattern of la(.-). The overall ET rate constants (K-r(DMN) = 0.99 x 10(10) M-1 s(-1) and k(r)(DMA) = 1.62 x 10(10) M-1 s(-1)) and limiting quantum yields (phi(lim)DMN) = 0.034 and phi(lim)(DMA) = 0.12) are estimated from the inverse plot (1/[la] vs 1/phi(dis)) Obtained by measuring the dependence of photodissociation quantum yields of la at its maximum concentration in the presence of DMN or DMA. Silicon-centered radical species generated from the mesolysis of la(.-) are utilized for initiating a radical reaction by the abstraction of halogen atom from -C-X (X = Cl, Br) bonds, while PhSe- terminates the radical sequences via PhSeSePh. This concept is successfully applied for the bimolecular group transfer (BMGT) radical reactions and intermolecular radical chain addition reactions.
• Pandey, Ganesh; Rao, K.S. Sesha Poleshwar, Angewandte Chemie, 1995, vol. 107, # 23/24, p. 2934 - 2935
  作者：Pandey, Ganesh、Rao, K.S. Sesha Poleshwar

  DOI：——

  日期：——
• J. ORG. CHEM., 1981, 46, N 7, 1283-1292
  作者：

  DOI：——

  日期：——
• Silyl halides from (phenylseleno)silanes. Reaction with oxiranes and alcohols to give hydrolytically stable silyl ethers
  作者：Michael R. Detty、Mark D. Seidler

  DOI：10.1021/jo00320a012

  日期：1981.3