(2-(bromomethyl)-4-methylphenoxy)(tert-butyl)dimethylsilane | 1268266-44-9

• 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-(bromomethyl)-4-methylphenoxy)(tert-butyl)dimethylsilane
• 英文别名: 2-bromomethyl-4-methyl-O-(tert-butyldimethylsilyl)phenol；[2-(Bromomethyl)-4-methylphenoxy]-tert-butyl-dimethylsilane；[2-(bromomethyl)-4-methylphenoxy]-tert-butyl-dimethylsilane
• CAS: 1268266-44-9
• 化学式: C₁₄H₂₃BrOSi
• 分子量: 315.326
• InChiKey: LBYYUGPLSSPIJX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.27
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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-(bromomethyl)-4-methylphenoxy)(tert-butyl)dimethylsilane 在 potassium fluoride 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  Oxidative Quenching of Quinone Methide Adducts Reveals Transient Products of Reversible Alkylation in Duplex DNA

  摘要：

  ortho-Quinone methides (ortho-QM) and para-quinone methides are generated by xenobiotic metabolism of numerous compounds including environmental toxins and therapeutic agents. These intermediates are highly electrophilic and have the potential to alkylate DNA. Assessing their genotoxicity can be difficult when all or some of their resulting adducts form reversibly. Stable adducts are most easily detected but are not necessarily the most prevalent products formed initially as DNA repair commences. Selective oxidation of ortho-QM-DNA adducts by bis[(trifluoroacetoxy)iodo]benzene (BTI) rapidly quenches their reversibility to prevent QM regeneration and allows for observation of the kinetic products. The resulting derivatives persist through standard enzymatic digestion, chromatography, and mass spectral analysis. The structural standards required for this approach have been synthesized and confirmed by two-dimensional NMR spectroscopy. The adducts of dA N-6, dG NI, dG N-2, and guanine N7 are converted to the expected para-quinol derivatives within 5 min after addition of BTI under aqueous conditions (pH 7). Concurrently, the adduct of dA N1 forms a Spiro derivative comparable to that characterized previously after oxidation of the corresponding dC N3 adduct. By application of this oxidative quenching strategy, the dC N3 and dA NI adducts have been identified as the dominant products formed by both single- and double-stranded DNA under initial conditions. As expected, however, these labile adducts dissipate within 24 h if not quenched with BTI. Still, the products favored by kinetics are responsible for inducing the first response to ortho-QM exposure in cells, and hence, they are also key to establishing the relationship between biological activity and molecular structure.

  DOI：

  10.1021/tx500152d
• 作为产物：
  描述：

  (2-(tert-butyldimethylsilyloxy)-5-methylphenyl)methanol 在 三溴化磷 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以55.8%的产率得到(2-(bromomethyl)-4-methylphenoxy)(tert-butyl)dimethylsilane
  参考文献：
  名称：

  捕获在邻-醌醌甲硫氨酸和2'-脱氧胞苷之间形成的不稳定加合物

  摘要：

  双[（三氟乙酰氧基）碘]苯（BTI）的选择性氧化为有效地捕集在生理条件下dC和邻醌甲基化物（QM）之间可逆形成的加合物提供了一个有效的陷阱。由4-甲基-o - QM和2'-脱氧胞苷生成的模型加合物通过分子内环化和芳香性的丧失迅速转化为用于量化QM烷基化的特征产物。然而，BTI引起了令人惊讶的重排，该重排是由在QM的4位缺少烷基取代基的衍生物的过氧化驱动的。

  DOI：

  10.1021/ol200071p

文献信息

• N-Heterocyclic carbene-catalyzed enantioselective annulations: a dual activation strategy for a formal [4+2] addition for dihydrocoumarins
  作者：Anna Lee、Karl A. Scheidt

  DOI：10.1039/c4cc09590a

  日期：——

  A highly efficient asymmetric formal [4+2] annulation for the synthesis of dihydrocoumarins has been developed via an in situ activated NHC catalysis. Both electrophilic and nucleophilic species are generated in situ simultaneously whereby acyl imidazoles facilitated rapid formation of an NHC-enolate intermediate to afford the [4+2] dihydrocoumarin adducts.

  通过原位活化的NHC催化，已经开发出了一种高效的不对称形式[4 + 2]正式环用于合成二氢香豆素。亲电物质和亲核物质同时在原位产生，因此酰基咪唑促进了NHC-烯醇酸酯中间体的快速形成，从而提供了[4 + 2]二氢香豆素加合物。
• Catalytic Asymmetric Synthesis of Chiral Dihydrobenzofurans through a Formal [4+1] Annulation Reaction of Sulfur Ylides and In Situ Generated<i>ortho</i>-Quinone Methides
  作者：Qing-Qing Yang、Wen-Jing Xiao

  DOI：10.1002/ejoc.201601186

  日期：2017.1.10

  The first example of a catalytic asymmetric formal [4+1] annulation reaction between sulfur ylides and in situ generated ortho-quinone methides (o-QMs) is reported in this work. A C2-symmetric chiral urea was identified to be the best H-bonding catalyst, affording a wide range of chiral 2,3-dihydrobenzofurans in high yields and moderate enantioselectivities [70–98 % yields, up to 89:11 e.r. (enantiomeric

  在这项工作中报道了硫叶立德与原位生成的邻醌甲基化物 (o-QMs) 之间的催化不对称形式 [4+1] 环化反应的第一个例子。一种 C2 对称手性尿素被认为是最好的 H 键合催化剂，可提供范围广泛的手性 2,3-二氢苯并呋喃，收率高，对映选择性适中 [70–98% 收率，高达 89:11 er )]。
• Oxidative Quenching of Quinone Methide Adducts Reveals Transient Products of Reversible Alkylation in Duplex DNA
  作者：Michael P. McCrane、Mark A. Hutchinson、Omer Ad、Steven E. Rokita

  DOI：10.1021/tx500152d

  日期：2014.7.21

  ortho-Quinone methides (ortho-QM) and para-quinone methides are generated by xenobiotic metabolism of numerous compounds including environmental toxins and therapeutic agents. These intermediates are highly electrophilic and have the potential to alkylate DNA. Assessing their genotoxicity can be difficult when all or some of their resulting adducts form reversibly. Stable adducts are most easily detected but are not necessarily the most prevalent products formed initially as DNA repair commences. Selective oxidation of ortho-QM-DNA adducts by bis[(trifluoroacetoxy)iodo]benzene (BTI) rapidly quenches their reversibility to prevent QM regeneration and allows for observation of the kinetic products. The resulting derivatives persist through standard enzymatic digestion, chromatography, and mass spectral analysis. The structural standards required for this approach have been synthesized and confirmed by two-dimensional NMR spectroscopy. The adducts of dA N-6, dG NI, dG N-2, and guanine N7 are converted to the expected para-quinol derivatives within 5 min after addition of BTI under aqueous conditions (pH 7). Concurrently, the adduct of dA N1 forms a Spiro derivative comparable to that characterized previously after oxidation of the corresponding dC N3 adduct. By application of this oxidative quenching strategy, the dC N3 and dA NI adducts have been identified as the dominant products formed by both single- and double-stranded DNA under initial conditions. As expected, however, these labile adducts dissipate within 24 h if not quenched with BTI. Still, the products favored by kinetics are responsible for inducing the first response to ortho-QM exposure in cells, and hence, they are also key to establishing the relationship between biological activity and molecular structure.
• Trapping a Labile Adduct Formed between an <i>ortho</i>-Quinone Methide and 2′-Deoxycytidine
  作者：Michael P. McCrane、Emily E. Weinert、Ying Lin、Eugene P. Mazzola、Yiu-Fai Lam、Peter F. Scholl、Steven E. Rokita

  DOI：10.1021/ol200071p

  日期：2011.3.4

  Selective oxidation by bis[(trifluoroacetoxy)iodo]benzene (BTI) provides an effective trap for quenching adducts formed reversibly between dC and an ortho-quinone methide (QM) under physiological conditions. A model adduct generated by 4-methyl-o-QM and 2′-deoxycytidine is rapidly converted by intramolecular cyclization and loss of aromaticity to a characteristic product for quantifying QM alkylation

  双[（三氟乙酰氧基）碘]苯（BTI）的选择性氧化为有效地捕集在生理条件下dC和邻醌甲基化物（QM）之间可逆形成的加合物提供了一个有效的陷阱。由4-甲基-o - QM和2'-脱氧胞苷生成的模型加合物通过分子内环化和芳香性的丧失迅速转化为用于量化QM烷基化的特征产物。然而，BTI引起了令人惊讶的重排，该重排是由在QM的4位缺少烷基取代基的衍生物的过氧化驱动的。