tert-butylchlorobis(4-methoxyphenyl)silane | 1394170-50-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: tert-butylchlorobis(4-methoxyphenyl)silane
• 英文别名: Tert-butyl-chloro-bis(4-methoxyphenyl)silane；tert-butyl-chloro-bis(4-methoxyphenyl)silane
• CAS: 1394170-50-3
• 化学式: C₁₈H₂₃ClO₂Si
• 分子量: 334.918
• InChiKey: WBGURHWPDAWVLK-UHFFFAOYSA-N

物化性质

• 沸点：
  401.9±30.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butylchlorobis(4-methoxyphenyl)silane 在 咪唑 、 甲醇 、 碘苯二乙酸 、 二异丁基氢化铝 、 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.03h， 生成 1-(2-((tert-butyl((1,1,1,3,3,3-hexafluoropropan-2-yl)oxy)(4-methoxyphenyl)silyl)oxy)ethyl)-4'-methoxy-1,4-dihydro-[1,1'-biphenyl]-4-ol
  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：

  4-溴苯甲醚 、 叔丁基锂 在 叔丁基三氯硅烷 作用下， 以 四氢呋喃 为溶剂， 生成 tert-butylchlorobis(4-methoxyphenyl)silane
  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

文献信息

• 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".
• 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.