tert-Butyl-chloro-di-p-tolyl-silane | 195608-69-6

• 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: tert-Butyl-chloro-di-p-tolyl-silane
• 英文别名: tert-butyl-chloro-bis(4-methylphenyl)silane
• CAS: 195608-69-6
• 化学式: C₁₈H₂₃ClSi
• 分子量: 302.919
• InChiKey: IWFCMWCZYCONOK-UHFFFAOYSA-N

物化性质

• 沸点：
  363.7±31.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  tert-Butyl-chloro-di-p-tolyl-silane 在 咪唑 、 甲醇 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 4-[2-[Tert-butyl-bis(4-methylphenyl)silyl]oxyethyl]phenol
  参考文献：
  名称：

  Oxidative ipso-Rearrangement Performed by a Hypervalent Iodine Reagent and Its Application

  摘要：

  An oxidative ipso-rearrangement mediated by a hypervalent iodine reagent that enables rapid generation of a functionalized dienone system containing a quaternary carbon center connected to several sp(2) centers has been developed. The process occurs through transfer of an aryl group from a silyl segment present on the lateral chain. As an illustration of the potential of this transformation, a total synthesis of sceletenone, a small alkaloid, is described.

  DOI：

  10.1021/jo301408j
• 作为产物：
  描述：

  tert-Butyl-di-p-tolyl-silane 在 过氧化苯甲酰 作用下， 以 四氯化碳 为溶剂， 反应 24.0h， 以88%的产率得到tert-Butyl-chloro-di-p-tolyl-silane
  参考文献：
  名称：

  Photochemical functionalizations of C60 with phenylpolysilanes

  摘要：

  Photolyses of tert-butyl substituted disilanes 1a-1c, and 1i with C-60 result in the formation of 1,16-adduct 2 through silyl radical addition to fullerene. The unusual products, 3, 5, 6 and 7 where the silyl and phenyl groups attached on 1,2-positions of fullerene are also obtained from the reaction of 1d-g and 4. The structures of all these compounds were determined by one- and two-dimensional NMR techniques. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00422-7

文献信息

• Desymmetrization‐Oriented Enantioselective Synthesis of Silicon‐Stereogenic Silanes by Palladium‐Catalyzed C−H Olefinations
  作者：Yan Lin、Wei‐Yang Ma、Zheng Xu、Zhan‐Jiang Zheng、Jian Cao、Ke‐Fang Yang、Yu‐Ming Cui、Li‐Wen Xu

  DOI：10.1002/asia.201900408

  日期：2019.6.14

  A palladium‐catalyzed chelation‐assisted enantioselective C−H olefination of symmetrically diaryl‐substituted tetraorganosilicon derivatives was developed, enabling the generation of nitrogen‐containing silicon‐stereogenic tetraorganosilicon compounds with modest to good yields and good to excellent enantioselectivities (up to 95.5:4.5 e.r.). The Thorpe–Ingold effect exerted by the substituents on

  已开发出钯催化的对称二芳基取代的四有机硅衍生物的螯合辅助对映选择性C H烯化反应，能够生成产率适中至良好且优良至优异对映选择性的含氮硅立体异构四有机硅化合物（高达95.5：4.5） er）。观察到，取代基在硅上产生的索普-英戈尔德效应对烯化产物的形成有深远的影响，该产物进一步转化为其他相关的手性有机硅烷，而不会损失对映体纯度，因此证明了已开发的对映选择性烯化的合成效用。
• Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles
  作者：Wan‐Er Gan、Yong‐Shun Wu、Bin Wu、Chun‐Yuan Fang、Jian Cao、Zheng Xu、Li‐Wen Xu

  DOI：10.1002/anie.202317973

  日期：2024.2.12

  A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via intramolecular Si−O coupling of [2‐(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si−C bond cleavage and Si−O bond formation. In addition, kinetic resolution of racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine‐oxazoline ligands) as the catalytic system is developed to afford carbon‐ and silicon‐stereogenic benzoxasiloles. Ring‐opening reactions of chiral benzoxasiloles with organolithiums and Grignard reagents yield various enantioenriched functionalized tetraorganosilanes.

  摘要 通过[2-(羟甲基)苯基]硅烷的分子内Si-O偶联，实现了铜催化的苯并噁唑类硅烷的不对称合成。研究发现，Cu(I)/二氟吗啉是对映体选择性 Si-C 键裂解和 Si-O 键形成的高效催化体系。此外，利用 Cu(I)/PyrOx（吡啶-噁唑啉配体）作为催化体系，开发了外消旋取代的[2-（羟甲基）苯基]硅烷的动力学解析，从而得到碳和硅稳定的苯并噁唑。手性苯并噁唑基硅烷与有机锂和格氏试剂的开环反应生成了各种对映体富集的官能化四有机硅烷。
• Rhodium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Dibenzooxasilines via Enantioselective Transmetalation
  作者：Ryo Shintani、Eleanor E. Maciver、Fumiko Tamakuni、Tamio Hayashi

  DOI：10.1021/ja3076555

  日期：2012.10.17

  A rhodium-catalyzed asymmetric synthesis of silicon-stereogenic dibenzooxasilines has been developed. High enantioselectivities have been achieved by employing (S,S)-Me-Duphos as the ligand through "enantioselective transmetalation".
• Substituents effects on the addition of silyllithium and germyllithium to C60
  作者：Takahiro Kusukawa、Wataru Ando

  DOI：10.1016/s0022-328x(98)00497-5

  日期：1998.6

  Mono-adducts 2 and di-adducts 3 are obtained by the reaction with silyllithium and germyllithium 1 with C-60. The selectivities of the products are controlled by electronic and steric effects of the substituents. Formations of 1,4-adduct 4 and dimer 5 can be obtained in the presence of biphenyl derivatives. (C) 1998 Elsevier Science S.A. All rights reserved.
• Construction of Si‐Stereogenic Silanols by Palladium‐Catalyzed Enantioselective C−H Alkenylation
  作者：Jia‐Hui Zhao、Long Zheng、Jian‐Ye Zou、Sheng‐Ye Zhang、Hua‐Chen Shen、Yichen Wu、Peng Wang

  DOI：10.1002/anie.202402612

  日期：2024.5.13

  The construction of silicon‐stereogenic silanols via Pd‐catalyzed intermolecular C−H alkenylation with the assistance of a commercially available L‐pyroglutamic acid has been realized for the first time. Employing oxime ether as the directing group, silicon‐stereogenic silanol derivatives could be readily prepared with excellent enantioselectivities, featuring a broad substrate scope and good functional group tolerance. Moreover, parallel kinetic resolution with unsymmetric substrates further highlighted the generality of this protocol. Mechanistic studies indicate that L‐pyroglutamic acid could stabilize the Pd catalyst and provide excellent chiral induction. Preliminary computational studies unveil the origin of the enantioselectivity in the C−H bond activation step.