2,2,6,6-tetramethylpiperidin-1-yl diphenylphosphinate | 112537-94-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 2,2,6,6-tetramethylpiperidin-1-yl diphenylphosphinate
• 英文别名: 1-Diphenylphosphoryloxy-2,2,6,6-tetramethylpiperidine
• CAS: 112537-94-7
• 化学式: C₂₁H₂₈NO₂P
• 分子量: 357.433
• InChiKey: CCXKETGVQOAUNG-UHFFFAOYSA-N

物化性质

• 沸点：
  438.8±28.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (1-(2,6-dimethylphenoxy)buta-2,3-dien-2-yl)diphenylphosphine oxide 在 四(三苯基膦)钯 、 sodium carbonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 54.0h， 生成 2,2,6,6-tetramethylpiperidin-1-yl diphenylphosphinate
  参考文献：
  名称：

  通过钯催化和可见光驱动的 C(sp3)–P(V) 裂解中继策略获得聚芳基联吡唑

  摘要：

  提出了一种前所未有的钯催化和可见光驱动的烯基氧化膦与原位生成的腈亚胺的中继反应，用于直接合成高价值的聚芳基联吡唑骨架。这种一锅策略涉及在无光催化剂且温和的反应条件下进行双 1,3-偶极环加成和 C(sp 3 )–P(V) 键断裂。该方法操作简单、步骤经济性高、底物范围广，能够以中等至优异的产率提供相应的产物。

  DOI：

  10.1021/acs.orglett.4c00503

文献信息

• A scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with RSH/ROH
  作者：Yujun Li、Qi Yang、Liquan Yang、Ning Lei、Ke Zheng

  DOI：10.1039/c9cc01378d

  日期：——

  A practical, scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with thiols, phenols and alcohols in both an undivided cell and a continuous-flow setup is disclosed. Its broad substrate scope (>50 examples), good functional-group tolerance and scalability (>10 g) show potential for practical synthesis. A preliminary mechanistic study suggests that the phosphorus radicals are

  公开了在不分开的电池和连续流动装置中P（O）H化合物与硫醇，酚和醇的实用的，可扩展的电化学脱氢交叉偶联。其广泛的底物范围（> 50个实例），良好的官能团耐受性和可扩展性（> 10 g）显示出可以进行实际合成的潜力。初步的机理研究表明，磷自由基参与了催化循环。
• Visible-Light-Promoted Transition-Metal-Free Phosphinylation of Heteroaryl Halides in the Presence of Potassium <i>tert</i>-Butoxide
  作者：Jia Yuan、Wai-Pong To、Zi-Yang Zhang、Chang-Duo Yue、Sixuan Meng、Jian Chen、Yungen Liu、Guang-Ao Yu、Chi-Ming Che

  DOI：10.1021/acs.orglett.8b03265

  日期：2018.12.21

  visible-light-promoted C–P bond formation reaction in the absence of both transition metal and photoredox catalysts is disclosed. By employing easily available and inexpensive heteroaryl chlorides/bromides as substrates, a variety of heteroaryl phosphine oxides were obtained in moderate to good yields. This strategy provides a simple and efficient route to heteroaryl phosphine oxides.

  公开了一种在不存在过渡金属和光氧化还原催化剂的情况下新型的可见光促进的C-P键形成反应。通过使用容易获得且便宜的杂芳基氯化物/溴化物作为底物，以中等至良好的产率获得了各种杂芳基氧化膦。该策略提供了简单且有效的制备杂芳基膦氧化物的途径。
• Copper catalyzed one-pot synthesis of β-ketophosphine oxides from ketones and H-phosphine oxides
  作者：Zhi-Jie Zhang、Dong Yi、Qiang Fu、Wu Liang、Su-Yuan Chen、Lu Yang、Feng-Tian Du、Jian-Xin Ji、Wei Wei

  DOI：10.1016/j.tetlet.2017.05.005

  日期：2017.6

  efficient copper catalyzed one-pot method has been developed for the formation of β-ketophosphine oxides from ketones and H-phosphine oxides under air at room temperature, in which vinylhydrazinedicarboxylate was formed as the key intermediate. Preliminary mechanistic studies indicated that the reaction might involve a radical process and carbonyl oxygen atom of β-ketophosphine oxides came from molecular

  已开发出一种简便有效的铜催化一锅法，用于在室温和空气中由酮和H-膦氧化物形成β-酮膦氧化物，其中乙烯基肼二羧酸酯是关键中间体。初步的机理研究表明，该反应可能涉及自由基过程，β-酮膦氧化物的羰基氧原子来自分子氧。
• Silver-Catalyzed Radical Arylphosphorylation of Unactivated Alkenes: Synthesis of 3-Phosphonoalkyl Indolines
  作者：Deqiang Liang、Dandan Ge、Yanping Lv、Wenzhong Huang、Baoling Wang、Weili Li

  DOI：10.1021/acs.joc.8b00450

  日期：2018.4.20

  A silver-catalyzed phosphorylation/cyclization cascade of N-allyl anilines was developed, allowing direct access to 3-phosphonoalkyl indolines, which were previously obtainable only via tedious procedures under harsh/toxic conditions. The unactivated double bond serves as the radical acceptor, whereas H-phosphonates or -phosphine oxides act as the radical precursor. This protocol features simple operation

  已开发出N-烯丙基苯胺的银催化磷酸化/环化级联反应，可直接使用3-膦酰基烷基二氢吲哚，以前只能通过在苛刻/有毒条件下繁琐的程序才能获得这些二氢吲哚。未活化的双键充当自由基受体，而H-膦酸酯或-膦氧化物充当自由基前体。这个协议提供操作简单，广泛的底物范围和大外型选择性，和克规模合成可以容易地进行。
• Visible-light-promoted organic dye-catalyzed sulfidation and phosphorylation of arylhydrazines toward aromatic sulfides and diarylphosphoryl hydrazides
  作者：Rui Li、Tao Shi、Xiao-Lan Chen、Qi-Yan Lv、Yin-Li Zhang、Yu-Yu Peng、Ling-Bo Qu、Bing Yu

  DOI：10.1039/c9nj03692j

  日期：——

  Visible-light-promoted sulfidation and phosphorylation of arylhydrazines for the synthesis of aromatic sulfides and diarylphosphoryl hydrazides were developed using the organic dyes rose bengal and Na2-eosin Y as photocatalysts, respectively. This strategy offers an efficient and mild transition-metal-free synthetic protocol for the formation of C–S and N–P bonds from arylhydrazines.

  使用有机染料玫瑰红和Na 2-曙红Y分别开发了可见光促进的芳基肼的硫化和磷酸化反应，用于合成芳族硫化物和二芳基磷酰肼。该策略为由芳基肼形成C–S和N–P键提供了有效且温和的无过渡金属合成方案。