[4-[[(tert-butyldimethylsilyl)oxy]methyl]phenyl]magnesium bromide | 107556-40-1

• 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: [4-[[(tert-butyldimethylsilyl)oxy]methyl]phenyl]magnesium bromide
• 英文别名: <4-<<(tert-butyldimethylsilyl)oxy>methyl>phenyl>magnesium bromide；(4-{[(tert-butyldimethylsilyl)oxy]methyl}phenyl)magnesium bromide；4-[(tert-butyldimethylsilyloxy)methyl]phenylmagnesium bromide
• CAS: 107556-40-1
• 化学式: C₁₃H₂₁BrMgOSi
• 分子量: 325.604
• InChiKey: MTHYCHZNRZVBHA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [4-[[(tert-butyldimethylsilyl)oxy]methyl]phenyl]magnesium bromide 在 氢氧化钾 、 氢氟酸 、 tetramethylammonium hydrogen difluoride 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 8.0h， 生成 (S)-α-hydroxy-α-<4-(fluoromethyl)phenyl>benzeneacetic acid
  参考文献：
  名称：

  Syntheses and Biological Properties of Chiral Fluoroalkyl Quinuclidinyl Benzilates

  摘要：

  Previously, (R)-quinuclidinyl (R)-4-iodobenzilate ((R,R)-IQNB), a muscarinic receptor antagonist, has been labeled with I-123 and I-125 for use in in vitro and in vivo studies in animals and humans. We have prepared fluoroalkyl analogs of QNB, which are amenable to labeling with F-18, for potential imaging applications with positron emission tomography. The enantiomers of (fluoroalkyl)benzilic acids were prepared via an enantioselective Grignard addition reaction. Subsequent coupling of the enantiomeric (fluoroalkyl)benzilic acid with a selected enantiomer of quinuclidinol provides fluorinated analogs of QNB with known stereochemistry at each of the stereogenic centers. These compounds exhibit different affinities for the muscarinic receptor tissue subtypes in vitro. (R,R)-4-(Fluoromethyl)-QNB, (R,R)-IQNB, and (R,R)-4-(fluoroethyl)-QNB exhibit selectivity for the M1 subtype, and (R,S)-4-(fluoromethyl)-QNB exhibits selectivity for the M2 subtype.

  DOI：

  10.1021/jm00010a016

文献信息

• The para-siletanylbenzyl (PSB) ether: a peroxide-cleavable protecting group for alcohols and phenols
  作者：Hubert Lam、Sarah E. House、Gregory B. Dudley

  DOI：10.1016/j.tetlet.2005.03.110

  日期：2005.5

  cleaved under mild oxidizing conditions in the presence of para-methoxybenzyl (PMB) is described herein. para-Siletanylbenzyl (PSB) ethers are formed in one or two steps from the corresponding alcohols and cleaved in one or two steps with basic peroxide. Alcohols and phenols have been protected in good yields and deprotected cleanly under mild oxidative conditions.

  本文描述了新颖的芳基甲基保护基，其在电子上类似于苄基（Bn），但是可以在存在对-甲氧基苄基（PMB）的情况下在温和的氧化条件下裂解。对-Siletanyl苄基（PSB）醚是由相应的醇在一两步中形成的，并在一两步中用碱性过氧化物裂解。醇和酚的收率很高，在温和的氧化条件下也可以干净地脱保护。
• Structure-activity relationships in the 2-arylcarbapenem series. Synthesis of 1-methyl-2-arylcarbapenems
  作者：Ravindra Nath Guthikonda、L. D. Cama、M. Quesada、M. F. Woods、T. N. Salzmann、B. G. Christensen

  DOI：10.1021/jm00388a022

  日期：1987.5

  tert-butyldimethylsilyl esters of the azetidinones 6-8b served as the crucial synthons in the preparation of the potentially useful ylide pyridyl thio esters 18-20. These intermediates were utilized to synthesize a host of title carbapenems 25-30d, 32, and 49-53. The antimicrobial properties and DHP-I susceptibility of these carbapenems were studied with reference to thienamycin.

  氮杂环丁酮6-8b的不稳定的叔丁基二甲基甲硅烷基酯在制备潜在有用的内酯吡啶基硫代硫酯18-20中起关键的合成子作用。这些中间体被用来合成许多标题碳青霉烯25-30d，32和49-53。参照噻菌霉素研究了这些碳青霉烯类的抗菌特性和DHP-1敏感性。
• Nickel-Catalyzed Dearomative <i>trans</i>-1,2-Carboamination
  作者：Lucas W. Hernandez、Ulrich Klöckner、Jola Pospech、Lilian Hauss、David Sarlah

  DOI：10.1021/jacs.8b01726

  日期：2018.4.4

  We describe the development of an arenophile-mediated, nickel-catalyzed dearomative trans-1,2-carboamination protocol. A range of readily available aromatic compounds was converted to the corresponding dienes using Grignard reagents as nucleophiles. This strategy provided products with exclusive trans-selectivity and high enantioselectivity was observed in case of benzene and naphthalene. The utility

  我们描述了亲盐介导的、镍催化的脱芳基 trans-1,2-carboamination 协议的发展。使用格氏试剂作为亲核试剂将一系列容易获得的芳族化合物转化为相应的二烯。在苯和萘的情况下，该策略提供了具有独家反式选择性和高对映选择性的产品。通过可控和立体选择性地制备功能化的小分子，展示了这种方法的实用性。
• Synthesis of a fluorescent steroid derivative with high affinities for the glucocorticoid and progesterone receptors
  作者：G TEUTSCH、M KLICH、F BOUCHOUX、E CEREDE、D PHILIBERT

  DOI：10.1016/0039-128x(94)90040-x

  日期：1994.1

  The synthesis of RU 45196, an 11 beta-substituted 19-norsteroid of the estra-4,9-diene series, incorporating the nitrobenzoxadiazole (NBD) fluorophore, is reported. The highly fluorescent target compound displayed remarkable affinity for both the progesterone and glucocorticoid receptors. The present work demonstrates for the first time that it is indeed possible to design fluorescent steroid conjugates which maintain very high affinities for their cognate receptors and which are potentially useful for mechanistic and diagnostic purposes.
• Structure−Activity Relationships of Selective Estrogen Receptor Modulators:  Modifications to the 2-Arylbenzothiophene Core of Raloxifene
  作者：Timothy A. Grese、Stephen Cho、Don R. Finley、Alexander G. Godfrey、Charles D. Jones、Charles W. Lugar、Michael J. Martin、Ken Matsumoto、Lewis D. Pennington、Mark A. Winter、M. Dee Adrian、Harlan W. Cole、David E. Magee、D. Lynn Phillips、Ellen R. Rowley、Lorri L. Short、Andrew L. Glasebrook、Henry U. Bryant

  DOI：10.1021/jm9606352

  日期：1997.1.1

  The 8-arylbenzothiophene raloxifene, 1, is a selective estrogen receptor modulator which is currently under clinical evaluation for the prevention and treatment of postmenopausal osteoporosis. A series of raloxifene analogs which contain modifications to the 2-arylbenzothiophene core have been prepared and evaluated for the ability to bind to the estrogen receptor and inhibit MCF-7 breast cancer cell proliferation in vitro. Their ability to function as tissue-selective estrogen agonists in vivo has been assayed in a short-term, ovariectomized (OVX) rat model with end points of serum cholesterol lowering, uterine weight gain, and uterine eosinophil peroxidase activity. These studies have demonstrated that (1) the 6-hydroxy and, to a lesser extent, the 4'-hydroxy substituents of raloxifene are important for receptor binding and in vitro activity, (2) small, highly electronegative 4'-substituents such as hydroxy, fluoro, and chloro are preferred both in vitro and in vivo, (3) increased steric bulk at the 4'-position leads to increased uterine stimulation in, vivo, and (4) additional substitution of the 2-aryl moiety is tolerated while additional substitution at the 4-, 5-, or 7-position of the benzothiophene results in reduced biological activity. In addition, compounds in which the 2-aryl group is replaced by alkyl, cycloalkyl, and naphthyl substituents maintain a profile of in vitro and in vivo biological activity qualitatively similar to that of raloxifene. Several novel structural variants including 2-cyclohexyl, 2-naphthyl, and 6-carbomethoxy analogs also demonstrated efficacy in preventing bone loss in a chronic OVX rat model of postmenopausal osteopenia, at doses of 0.1-10 mg/kg.