2,4-di-O-tert-butyldimethylsiloxybenzaldehyde | 122005-12-3

• 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: 2,4-di-O-tert-butyldimethylsiloxybenzaldehyde
• 英文别名: 2,4-di(t-butyldimethylsilyloxy)benzaldehyde；2,4-Bis[[tert-butyl(dimethyl)silyl]oxy]benzaldehyde
• CAS: 122005-12-3
• 化学式: C₁₉H₃₄O₃Si₂
• 分子量: 366.648
• InChiKey: CAQARUARBPOVSK-UHFFFAOYSA-N

物化性质

• 沸点：
  375.0±37.0 °C(Predicted)
• 密度：
  0.950±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.27
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,4-di-O-tert-butyldimethylsiloxybenzaldehyde 在 zinc(II) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 以91%的产率得到4-((tert-butyldimethylsilyl)oxy)-2-hydroxybenzaldehyde
  参考文献：
  名称：

  Positional chemoselectivity in the Zn(II)-mediated removal of phenol protecting groups

  摘要：

  A protocol was developed for the chemoselective ortho-deprotection of polyphenolic substrates using readily available (ZnX2)-X-II salts. This procedure provides exceptional positional selectivity for the deprotection of phenols that reside adjacent to directing carbonyl functionality in the presence of similar protecting groups at the meta and para positions. Good to excellent yields of the desired free phenols were obtained (<= 96%), and a wide assortment of protecting groups was readily removed under the reaction conditions. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.07.103
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 2,4-二羟基苯甲醛 在 二异丙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.33h， 以99.8%的产率得到2,4-di-O-tert-butyldimethylsiloxybenzaldehyde
  参考文献：
  名称：

  环呋喃，抗真菌苯并呋喃及一些相关类似物的合成

  摘要：

  研究了从野生鹰嘴豆中合成羟基化的苯并呋喃类化合物cicerfuran的途径，其中涉及抗枯萎病枯萎病及其一些类似物。描述了一种新的方法，用于通过2'-羟基苯乙烯的环氧化和环化合成氧化的苯并呋喃。所需的二苯乙烯中间体可以通过钯催化的苯乙烯与单加氧的芳基卤化物而不是与二加氧的芳基卤化物偶合而合成。通过维蒂希反应合成了对应于后者的二苯乙烯。

  DOI：

  10.1016/j.tet.2006.02.015

文献信息

• A New and Efficient Synthesis of Substituted 2-Hydroxymethyl-2-methyl-2H-chromenes
  作者：J. Y. Goujon、F. Zammattio、S. Pagnoncelli、Y. Boursereau、B. Kirschleger

  DOI：10.1055/s-2002-19763

  日期：——

  A new and efficient three step procedure for the synthesis of functionalized 2H-chromenes 1 is described, starting from commercially available salicylaldehydes 2 and 2-methylpropenylmagnesium chloride 3, which involves catalytic acid-mediated intramolecular cyclization of phenolic epoxide 5 as the key step.

  描述了一种新颖高效的三步合成官能团化2H-克罗门1的方法，起始于市售的水杨醛2和2-甲基丙烯基氯化镁3，关键步骤是催化酸介导的酚类环氧化物5的分子内环化反应。
• Enantioselective Synthesis of Four Natural Homoisoflavonoids
  作者：Yan-Chao Yu、Shijun Zhu、Xiao-Wei Lu、Yikang Wu、Bo Liu

  DOI：10.1002/ejoc.201500579

  日期：2015.8

  Four naturally occurring sappanin-type homoisoflavonoids were synthesized in optically active form with the stereogenic centers of predefined absolute configuration constructed by using Evans' asymmetric aldol reaction. Analysis of the synthesized compounds not only confirmed the previously assigned planar structures but also was used to determine the absolute configurations of the natural products

  四种天然存在的 sappanin 型同型异黄酮以光学活性形式合成，具有使用 Evans 的不对称羟醛反应构建的预定义绝对构型的立体中心。对合成化合物的分析不仅证实了先前指定的平面结构，而且还用于确定天然产物的绝对构型。先前报告的 NMR 信号/溶剂中的错误也被揭示。
• An NIR Fluorescence Turn‐on and MRl Bimodal Probe for Concurrent Real‐time in vivo Sensing and Labeling of <i>β</i>‐Galactosidase
  作者：Qiao Yu、Lei Zhang、Mou Jiang、Long Xiao、Yunhui Xiang、Ruifang Wang、Zhaoqing Liu、Rui Zhou、Minghui Yang、Conggang Li、Maili Liu、Xin Zhou、Shizhen Chen

  DOI：10.1002/anie.202313137

  日期：2023.11.13

  To realize sensing and labeling biomarkers is quite challenging in terms of designing multimodal imaging probes. In this study, we developed a novel β‐galactosidase (β‐gal) activated bimodal imaging probe that combines near‐infrared (NIR) fluorescence and magnetic resonance imaging (MRI) to enable real‐time visualization of activity in living organisms. Upon β‐gal activation, Gal‐Cy‐Gd‐1 exhibits a remarkable 42‐fold increase in NIR fluorescence intensity at 717 nm, allowing covalent labeling of adjacent target enzymes or proteins and avoiding molecular escape to promote probe accumulation at the tumor site. This fluorescence reaction enhances the longitudinal relaxivity by approximately 1.9 times, facilitating high‐resolution MRI. The unique features of Gal‐Cy‐Gd‐1 enable real‐time and precise visualization of β‐gal activity in live tumor cells and mice. The probe's utilization aids in identifying in situ ovarian tumors, offering valuable assistance in the precise removal of tumor tissue during surgical procedures in mice. The fusion of NIR fluorescence and MRI activation through self‐immobilizing target enzymes or proteins provides a robust approach for visualizing β‐gal activity. Moreover, this approach sets the groundwork for developing other activatable bimodal probes, allowing real‐time in vivo imaging of enzyme activity and localization.

  摘要 要实现对生物标记物的传感和标记，在设计多模态成像探针方面具有相当大的挑战性。在这项研究中，我们开发了一种新型的β-半乳糖苷酶（β-gal）激活双模成像探针，它结合了近红外（NIR）荧光和磁共振成像（MRI）技术，可实现生物体内活动的实时可视化。β-gal激活后，Gal-Cy-Gd-1在717 nm波长处的近红外荧光强度显著增加42倍，可共价标记邻近的靶酶或蛋白质，避免分子逃逸，促进探针在肿瘤部位聚集。这种荧光反应将纵向弛豫性提高了约 1.9 倍，从而促进了高分辨率磁共振成像。Gal-Cy-Gd-1 的独特功能可以实时、精确地观察活体肿瘤细胞和小鼠体内的 β-gal 活性。探针的使用有助于识别原位卵巢肿瘤，为小鼠手术过程中精确切除肿瘤组织提供了宝贵的帮助。通过自固定靶酶或蛋白质将近红外荧光和核磁共振成像激活融合在一起，为β-gal活性的可视化提供了一种强有力的方法。此外，这种方法还为开发其他可激活的双模探针奠定了基础，从而可对酶的活性和定位进行实时体内成像。
• 基于甲基醌结构的半乳糖苷酶响应双模态探针Gal-Cy-Gd-1及其合成方法和应用
  申请人：中国科学院精密测量科学与技术创新研究院

  公开号：CN117886874A

  公开（公告）日：2024-04-16

  本发明公开了一种基于甲基酮结构的半乳糖苷酶响应荧光、磁共振双模态探针Gal‑Cy‑Gd‑1及其合成方法与应用，所述探针Gal‑Cy‑Gd‑1的结构式如下：#imgabs0#该探针本身具有相对较低的荧光信号和磁共振信号，但在半乳糖苷酶响应后，会发生一系列电子转移，形成甲基醌的中间体结构，这种甲基醌中间体结构反应活性很高，容易受到蛋白质外部残基亲核基团进攻，从而使探针锚定在半乳糖苷酶上，导致荧光信号和磁共振信号增强，延长药物的半衰期，扩大成像时间窗口，从而实现肿瘤的早期检测以及手术切除。
• An efficient one-pot oxidative esterification of aldehydes to carboxylic esters using B(C6F5)3–TBHP
  作者：Sravanthi Devi Guggilapu、Santosh Kumar Prajapti、Bathini Nagendra Babu

  DOI：10.1016/j.tetlet.2015.01.033

  日期：2015.2

  A simple and efficient protocol for oxidative esterification of diverse aldehydes with alcohols was accomplished with tert-butyl hydroperoxide and 1 mol % of tris(pentafluorophenyl)borane [B(C6F5)(3)] to generate the corresponding esters in good to excellent yields. The present protocol represents compatibility with wide range of functional groups as well as exceptional tolerance toward acid labile protecting groups such as TBDPS, TBDMS, acetonide, and Boc. (C) 2015 Elsevier Ltd. All rights reserved.