4-bromobenzyl-α,α-d₂ alcohol | 42006-91-7

• 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: 4-bromobenzyl-α,α-d₂ alcohol
• 英文别名: 4-Bromo-benzylalcohol (D2)；(4-bromophenyl)-dideuteriomethanol
• CAS: 42006-91-7
• 化学式: C₇H₇BrO
• 分子量: 189.02
• InChiKey: VEDDBHYQWFOITD-BFWBPSQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-bromobenzyl-α,α-d₂ alcohol 在 lithium aluminium tetrahydride 、 lithium aluminium deuteride 、 三溴化磷 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 8.75h， 生成 4-methyl-d3-benzyl alcohol
  参考文献：
  名称：

  用离子回旋双共振光谱法测定异构二甲苯的形成热

  摘要：

  使用脉冲离子回旋双共振光谱法测量了潘邻二甲苯的 50 和 53 kcal mol-' 的形成热。此外，对于气态间二甲苯的形成热，已经获得了 76 kcal mol-' 的下限。C6H6 碳氢化合物家族包括各种有趣且经过大量研究的化合物，其稳定性范围从苯乙烯到高度应变的立方烷。尚未分离的一系列 C6H6 异构体是二甲苯 (1-3)。

  DOI：

  10.1021/ja00411a007
• 作为产物：
  描述：

  4-溴苯甲酸 在 硼氘化钠 、 碘 作用下， 以 四氢呋喃 为溶剂， 以86 %的产率得到4-bromobenzyl-α,α-d₂ alcohol
  参考文献：
  名称：

  Hyperpolarization of 15N‐Pyridinium by Using Parahydrogen Enables Access to Reactive Oxygen Sensors and Pilot In Vivo Studies

  摘要：

  Magnetic resonance with hyperpolarized contrast agents is one of the most powerful and noninvasive imaging platforms capable for investigating in vivo metabolism. While most of the utilized hyperpolarized agents are based on 13C nuclei, a milestone advance in this area is the emergence of 15N hyperpolarized contrast agents. Currently, the reported 15N hyperpolarized agents mainly utilize the dissolution dynamic nuclear polarization (d‐DNP) protocol. The parahydrogen enhanced 15N probes have proven to be elusive and have been tested almost exclusively in organic solvents. Herein, we designed a reaction based reactive oxygen sensor 15N‐boronobenzyl‐2‐styrylpyridinium (15N‐BBSP) which can be hyperpolarized with para‐hydrogen. Reactive oxygen species plays a vital role as one of the essential intracellular signalling molecules. Disturbance of the H2O2 level usually represents a hallmark of pathophysiological conditions. This H2O2 probe exhibited rapid responsiveness toward H2O2 and offered spectrally resolvable chemical shifts. We also provide strategies to bring the newly developed probe from the organic reaction solution into a biocompatible injection buffer and demonstrate the feasibility of in vivo 15N signal detection. The present work manifests its great potential not only for reaction based reactive sensing probes but also promises to serve as a platform to develop other contrast agents.

  DOI：

  10.1002/anie.202403144

文献信息

• 一种氘代的异恶唑类化合物的制备方法和用途
  申请人：朱允涛

  公开号：CN110776505A

  公开（公告）日：2020-02-11

  本发明公开了如式(I)所示的氘代异恶唑类化合物或其前药的制备方法和用途。本发明所述的氘代异恶唑类化合物及其前药可作为真菌GPI锚定蛋白合成酶抑制剂应用于抗真菌感染药物方面。
• Regioselective Hydrohydroxyalkylation of Styrene with Primary Alcohols or Aldehydes via Ruthenium-Catalyzed C−C Bond Forming Transfer Hydrogenation
  作者：Hongde Xiao、Gang Wang、Michael J. Krische

  DOI：10.1002/anie.201609056

  日期：2016.12.23

  Transfer hydrogenative coupling of styrene with primary alcohols using the precatalyst HClRu(CO)(PCy3)2 modified by AgOTf or HBF4 delivers branched or linear adducts from benzylic or aliphatic alcohols, respectively. Related 2‐propanol mediated reductive couplings also are described.

  使用经 AgOTf 或 HBF 4改性的预催化剂 HClRu(CO)(PCy 3 ) 2进行苯乙烯与伯醇的转移氢化偶联，分别产生来自苄醇或脂肪醇的支化或线性加合物。还描述了相关的 2-丙醇介导的还原偶联。
• Remarkable Substituent Effects on the Oxidizing Ability of Tetraarylbismuthonium Tetrafluoroborates in Alcohol Oxidation
  作者：Yoshihiro Matano、Takeshi Suzuki、Takaharu Iwata、Tomonori Shinokura、Hiroshi Imahori

  DOI：10.1246/bcsj.81.1621

  日期：2008.12.15

  Substituent effects on the oxidizing ability of tetraarylbismuthonium tetrafluoroborates in alcohol oxidation are reported. Intermolecular and intramolecular competition experiments on geraniol oxidation by the combined use of tetraarylbismuthonium tetrafluoroborates and N,N,N′,N′-tetramethylguanidine (TMG) have revealed that the oxidizing ability of the bismuthonium salt increases by the introduction of methyl groups at the ortho position and an electron-withdrawing group at the para position of the aryl ligands. The intermolecular and intramolecular H/D kinetic isotope effects observed for the competitive oxidation of p-bromobenzyl alcohols have shown that the present oxidation reaction consists of fast pre-equilibrium leading to alkoxytetraarylbismuth(V) intermediates (first step) and α-hydrogen abstraction by the aryl ligand attached to the bismuth (second step). The experimental results demonstrate that the electron-deficient aryl ligands enhance the electrophilicity at the bismuth center to put forward the first step and that the bulky ligands destabilize the alkoxybismuth(V) intermediates to accelerate the second step. The newly explored mesityl- and 2,6-xylyltriarylbismuthonium salts have proven to convert primary and secondary alcohols to the corresponding carbonyl compounds with high efficiency under mild conditions. A remarkable steric effect of these oxidants has also been exhibited in the chemoselective oxidation between primary and secondary benzylic alcohols.

  本文报道了四芳基铋鎓四氟硼酸盐在醇氧化中取代基效应对其氧化能力的影响。通过使用四芳基铋鎓四氟硼酸盐和N,N,N′,N′-四甲基胍（TMG）联合进行的香叶醇氧化分子间和分子内竞争实验揭示，当甲基引入芳基配体的邻位和吸电子基团引入对位时，铋鎓盐的氧化能力增强。在p-溴苯甲醇竞争氧化中观察到的分子间和分子内H/D动力学同位素效应表明，目前的氧化反应包括快速前置平衡，导致生成烷氧基四芳基铋(V)中间体（第一步）和与铋相连的芳基配体对α-氢的夺取（第二步）。实验结果表明，缺电子芳基配体增强了铋中心的亲电性，推动了第一步，而庞大的配体破坏了烷氧基铋(V)中间体的稳定性，加速了第二步。新探索的间甲苯基和2,6-二甲苯基三芳基铋鎓盐在温和条件下已被证明能高效地将伯醇和仲醇转化为相应的羰基化合物。这些氧化剂在伯醇和仲醇的化学选择性氧化中也表现出显著的立体效应。
• 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。
• Ruthenium-BINAP Catalyzed Alcohol C–H <i>tert</i>-Prenylation via 1,3-Enyne Transfer Hydrogenation: Beyond Stoichiometric Carbanions in Enantioselective Carbonyl Propargylation
  作者：Khoa D. Nguyen、Daniel Herkommer、Michael J. Krische

  DOI：10.1021/jacs.6b02279

  日期：2016.4.27

  found to catalyze the enantioselective C-C coupling of diverse primary alcohols with the 1,3-enyne, TMSC≡CC(Me)═CH2, to form secondary homopropargyl alcohols bearing gem-dimethyl groups. All reagents for this byproduct-free coupling are inexpensive and commercially available, making this protocol a practical alternative to stoichiometric carbanions in enantioselective carbonyl reverse prenylation.

  发现由 (TFA)2Ru(CO)(PPh3)2 和 (R)-BINAP 原位形成的手性钌配合物可催化多种伯醇与 1,3-烯炔的对映选择性 CC 偶联，TMSC≡CC(Me )=CH2，形成带有钋-二甲基基团的仲高炔丙醇。这种无副产品耦合的所有试剂都很便宜且可商购，使该协议成为对映选择性羰基反向异戊二烯化中化学计量碳负离子的实用替代品。