(2-Bromo-benzyloxy)-tert-butyl-diphenyl-silane | 132286-87-4

• 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: (2-Bromo-benzyloxy)-tert-butyl-diphenyl-silane
• 英文别名: (2-Bromophenyl)methoxy-tert-butyl-diphenylsilane
• CAS: 132286-87-4
• 化学式: C₂₃H₂₅BrOSi
• 分子量: 425.44
• InChiKey: AJQAGSFRASKGDK-UHFFFAOYSA-N

物化性质

• 沸点：
  451.5±37.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.53
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2-Bromo-benzyloxy)-tert-butyl-diphenyl-silane 在 N,N-二甲基丙烯基脲 、 四(三苯基膦)钯 、 四溴化碳 、 四甲基乙二胺 、 caesium carbonate 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  使用自组装手性双齿 P,P-配体的不对称催化

  摘要：

  描述了一种模块化催化剂开发策略，该策略基于结构金属周围双功能亚基的金属定向自组装以形成杂配复合物，其中第二组连接基团现在适当地布置以结合第二金属以形成催化位点. 手性二亚磷酸酯库是通过金属定向自组装制备的，并用于简单的不对称烯丙基胺化，产生高达 97% 的对映体过量。

  DOI：

  10.1021/ja049873+
• 作为产物：
  描述：

  2-溴苄醇 、 叔丁基二苯基氯硅烷 生成 (2-Bromo-benzyloxy)-tert-butyl-diphenyl-silane
  参考文献：
  名称：

  一个新的被保护的酰基保护基，用于核碱基的环外氨基官能团

  摘要：

  2-（叔丁基二苯基甲硅烷氧基甲基）苯甲酰氯（SiOMB-Cl）与过-O-三甲基甲硅烷基化的d-核苷C，G和A反应，除去Si（Me）3基团并进行5'-O-保护后得到含有4,4'-二甲氧基三苯甲基氯（DMT-Cl）的相应N-SiOMB-5'-O-DMT衍生物，其SiOMB基很容易被氟离子除去。SiOMB保护的核苷被证明是在溶液中和在固体支持物上制备DNA片段的合适构建单元。

  DOI：

  10.1016/s0040-4039(00)94573-8

文献信息

• Self-assembled heteroleptic chiral ligands, assymetric catalyst systems and methods
  申请人：Takacs M. James

  公开号：US20060167294A1

  公开（公告）日：2006-07-27

  A method of synthesizing a heteroleptic, multiple metal-containing metallocyclic catalyst, particularly suited for asymmetric catalysis, comprising combining a plurality of plural functional group-containing, monodentate ligands of complementary chirality, said plural functional groups being tethered to each other by tethers in the presence of a scaffold-structural metal Ms or derivative thereof, wherein at least one functional group on each ligand combines to ligate M s to form a bidentate, M s centered ligand scaffold containing the remaining functional groups and combining said bidentate ligand scaffold with a catalytic metal M c or derivative thereof whereby the remaining functional groups combine to ligate M c , thereby forming said catalyst.

  一种合成杂双核、含多金属的金属环催化剂的方法，特别适用于不对称催化，包括将多个含有多个功能基团的单齿配体以互补手性结合，所述多个功能基团通过连接体相互连接，在存在支架结构金属Ms或其衍生物的情况下，其中每个配体上至少一个功能基团结合以配位Msto形成双齿、以Ms为中心的配体支架，其中包含其余的功能基团，并将所述双齿配体支架与催化金属Mcor其衍生物结合，从而其余的功能基团结合以配位Mc，从而形成所述催化剂。
• 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。
• Synthesis of 2-aminobenzophenones via rapid halogen-lithium exchange in the presence of a 2-amino-N-methoxy-N-methylbenzamide
  作者：Stephen V. Frye、Marty C. Johnson、Nicole L. Valvano

  DOI：10.1021/jo00011a066

  日期：1991.5
• Nickel(0)-Catalyzed Enantio- and Diastereoselective Synthesis of Benzoxasiloles: Ligand-Controlled Switching from Inter- to Intramolecular Aryl-Transfer Process
  作者：Ravindra Kumar、Yoichi Hoshimoto、Hayato Yabuki、Masato Ohashi、Sensuke Ogoshi

  DOI：10.1021/jacs.5b07827

  日期：2015.9.16

  A highly enantioselective synthesis of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles (up to 99.9% ee and 99% yield) was achieved via the sequential activation of an aldehyde and a silane by nickel(0). This strategy was applied to a simultaneous generation of carbon- and silicon-stereogenic centers with excellent selectivity (dr = 99:1) via diastereotopic aryl transfer. Initial mechanistic studies revealed the complete switching of an aryl-transfer process from an intermolecular (racemic synthesis in the presence of IPr) to an intramolecular (enantioselective synthesis using chiral NHC, L5) fashion. A plausible rationale for the switching of the aryl-transfer process is given by a preliminary DFT calculation, which suggests that the coordination of 1 to the nickel(0)/L5 fragment in an eta(2)-arene:eta(2)-aldehyde fashion would be a key to the intramolecular process, while the formation of the corresponding intermediate is not possible in the presence of IPr. Owing to the chemically labile nature of its C-Si and O-Si bonds, enantioenriched benzoxasiloles are utilized for the synthesis of chiral building blocks and antihistaminic and anticholinergic drug molecules such as (R)-orphenadrine and (S)-neobenodine with no erosion of the enantiomeric excess.
• FRYE, STEPHEN V.;JOHNSON, MARTY C.;VALVANO, NICOLE L., J. ORG. CHEM., 56,(1991) N1, C. 3750-3752
  作者：FRYE, STEPHEN V.、JOHNSON, MARTY C.、VALVANO, NICOLE L.

  DOI：——

  日期：——