3-bromobenzaldehyde-α-d₁ | 71435-13-7

• 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: 3-bromobenzaldehyde-α-d₁
• 英文别名: (3-Bromophenyl)-deuteriomethanone
• CAS: 71435-13-7
• 化学式: C₇H₅BrO
• 分子量: 186.012
• InChiKey: SUISZCALMBHJQX-UICOGKGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.26
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-bromobenzaldehyde-α-d₁ 在 正丁基锂 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 38.0h， 生成
  参考文献：
  名称：

  Regiochemical Tagging:  A New Tool for Structural Characterization of Isomeric Components in Combinatorial Mixtures

  摘要：

  In this contribution we present a new combined synthetic and analytical strategy (regiochemical ragging) that allows facile determination of complete structure, including substituent position and regiochemistry, of mass-redundant components in complex combinatorial mixtures. The libraries of components (oxime ethers) are formed by the reaction of a mixture of substituents (aldehydes) with a scaffold containing several chemically similar attachment points (aminooxy groups), The structure of the resulting library components can then be determined from a combination of single MS and the tandem (MS/MS) spectra. Determination of the unique isomeric motif for each component is made possible via the following features of library design: (1) pan of the scafforld moiety, "transferable group" (the nitrogen atom from the oxime group) is transferred to the: substituent during fragmentation in the tandem experiment, (2) transferable groups on the scaffold differ from each other by either isotopic labels or fragmentation energies, and (3) mass-redundant substituents are isotopically labeled to create at least a 2 mass unit difference between them. The components of thr resulting library thus become labeled with different mass- and energy tags, which allows for precise regiochemical assignment of the functional group positions on the scaffold and substituents by mass spectrometry. The approach has been used to create and analyze a mixture of 27 isomeric compounds, each containing three boronic acid groups. The combination of the MS and MS/MS spectra of the tagged mixture has yielded a unique and structurally definitive signature of each component. Applications of the regiochemical tagging techniques to rapid synthesis and screening of combinatorial mixtures are discussed.

  DOI：

  10.1021/ja993844v
• 作为产物：
  描述：

  2-(3-溴苯基)-2-氧代乙酸 在 2,4,6-Triisopropylthiophenol 、 重水 、 四丁基醋酸铵 、 C₃₁H₃₀N⁽¹⁺⁾*BF₄^(1-) 作用下， 以 1,2-二氯乙烷 为溶剂， 以29.7 mg的产率得到3-bromobenzaldehyde-α-d₁
  参考文献：
  名称：

  可见光光氧化还原催化 α-氧代羧酸脱羧生成 C1-氘代醛和醛

  摘要：

  高附加值的 C1-氘代醛的合成将提高用于氘标记药物发现的氘化先导化合物的可用性。在此，我们开发了一种在环境温度下从 α-氧代羧酸中用 D 2 O无金属合成 C1-氘代醛的方法。通过可见光光氧化还原催化脱羧，避免了化学计量的还原剂和氧化剂。可以耐受各种官能团，并在温和条件下以高达 92% 的产率和 91-97% 的 D 掺入率产生 C1-氘醛。该方法也适用于各种醛的合成。主要机理研究表明，催化途径通过还原猝灭途径发生，然后是氢原子转移。

  DOI：

  10.1021/acs.joc.2c02299

文献信息

• [EN] SYNTHESIS OF DEUTERATED ALDEHYDES<br/>[FR] SYNTHÈSE D'ALDÉHYDES DEUTÉRÉS
  申请人：UNIV ARIZONA

  公开号：WO2021045879A1

  公开（公告）日：2021-03-11

  Described are methods for preparing a deuterated aldehyde using N-heterocyclic carbene catalysts in a solvent comprising D2O. The methods may be used to convert a wide variety of aldehydes (e.g., aryl, alkyl, or alkenyl aldehydes) to C-1 deuterated aldehydes under mild reaction conditions without functionality manipulation.

  描述了使用包含重水(D2O)的溶剂中的N-杂环卡宾催化剂来制备氘代乙醛的方法。这些方法可以在温和的反应条件下，不改变功能团的情况下，将各种乙醛（例如，芳香醛、脂肪醛或不饱和脂肪醛）转化为C-1位置氘代的乙醛。
• Iridium-Catalyzed Formyl-Selective Deuteration of Aldehydes
  作者：William J. Kerr、Marc Reid、Tell Tuttle

  DOI：10.1002/anie.201702997

  日期：2017.6.26

  for formyl‐selective deuterium labeling of aromatic aldehydes under mild conditions, using an iridium‐based catalyst designed to favor formyl over aromatic C−H activation. A good range of aromatic aldehydes is selectively labeled, and a one‐pot labeling/olefination method is also described. Computational studies support kinetic product control over competing aromatic labeling and decarbonylation pathways

  我们报告了第一种直接催化方法，该方法在温和条件下使用了基于铱的催化剂，旨在优先于甲酰胺而不是芳香族CH活化，从而在芳香族条件下对芳香族醛进行甲酰选择性氘标记。有选择地标记了各种芳香醛，并描述了一种单锅标记/烯烃化方法。计算研究支持动力学产品控制竞争性的芳香族标记和脱羰途径。
• Formyl-selective deuteration of aldehydes with D₂O <i>via</i> synergistic organic and photoredox catalysis
  作者：Jianyang Dong、Xiaochen Wang、Zhen Wang、Hongjian Song、Yuxiu Liu、Qingmin Wang

  DOI：10.1039/c9sc05132e

  日期：——

  Formyl-selective deuteration of aldehydes is of high interest for labeling purposes and for optimizing properties of drug candidates. Herein, we report a mild general method for formyl-selective deuterium labeling of aldehydes with D2O, an inexpensive deuterium source, via a synergistic combination of light-driven, polyoxometalate-facilitated hydrogen atom transfer and thiol catalysis. This highly

  醛的甲酰基选择性氘化对于标记目的和优化候选药物的性质具有重要意义。在这里，我们报告了一种温和的通用方法，通过光驱动、多金属氧酸盐促进的氢原子转移和硫醇催化的协同组合，用廉价的氘源D 2 O对醛进行甲酰基选择性氘标记。这种高效、可扩展的反应显示出优异的氘掺入、广泛的底物范围以及优异的官能团耐受性和选择性，因此是药物化学合成中间体后期修饰和生成氘代化合物库的实用方法。
• Photodeuterierung von benzaldehyd und substituierten benzaldehyden
  作者：Albert Defoin、Rosalie Defoin-Straathann、Hans Jochen Kuhn

  DOI：10.1016/s0040-4020(01)96882-6

  日期：1984.1

  In the presence of deuterium oxide benzaldehyde () and substituted benzaldehydes likewise possessing lowest triplet states of (n,w*) character yield formyl-deuteriated benzaldehydes by fast and efficient photoreactions. Quantum yields of formation of 7-deuterio benzaldehyde in solvent acetonitrile-deuterium oxide 3:1 are 0.57 at 313 nm), 0.54 at 331 nm. 0.62 at 365 nm, and in acetone-deuterium oxide

  在氧化氘苯甲醛（）和具有最低（n，w *）特征的三重态的取代苯甲醛的存在下，通过快速和有效的光反应也可制得甲酰基-氘代苯甲醛。在溶剂乙腈-氧化氘3：1中形成7-氘代苯甲醛的量子产率在313 nm下为0.57，在331 nm下为0.54。在365 nm处为0.62，在丙酮-氘化氧化物3：1中在313 nm下为0.87。在334 nm处为0.83，在365 nm处为0.91。副产品。主要是内消旋和dl-二氢安息香和安息香。仅在很小的程度上形成。在CIDNP测量的基础上，讨论了光氘的机理。
• Programmable iodization/deuterolysis sequences of phosphonium ylides to access deuterated benzyl iodides and aromatic aldehydes
  作者：Yu Zheng、Xian-Chen He、Jie Gao、Zhen-Zhen Xie、Zhi-Wei Wang、Zhi-Lin Liu、Kai Chen、Hao-Yue Xiang、Xiao-Qing Chen、Hua Yang

  DOI：10.1039/d2cc00537a

  日期：——

  Herein, a tunable iodization/deuterolysis protocol for phosphonium ylides by employing D2O as the deuterium source was designed. Notably, this process could be manipulated by tuning the base, thus leading to two valuable deuterated building blocks – benzyl iodides and aromatic aldehydes with broad substrate scope, good functional group compatibility and excellent deuteration degree. Concise syntheses

  在此，设计了一种采用 D 2 O 作为氘源的鏻叶立德的可调谐碘化/氘解方案。值得注意的是，这个过程可以通过调整碱基来控制，从而产生两个有价值的氘代结构单元——苄基碘和芳香醛，它们具有广泛的底物范围、良好的官能团相容性和优异的氘化度。基于开发的氘代反应平台，实现了一系列氘代药物类似物的简明合成。