α-(diethoxyphosphinyl)-δ-valerolactone | 122593-65-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: α-(diethoxyphosphinyl)-δ-valerolactone
• 英文别名: diethyl (2-oxotetrahydro-2H-pyran-3-yl)phosphonate；3-(diethoxyphosphinyl)tetrahydro-2H-pyran-2-one；Diethyl 2-oxotetrahydro-2H-pyran-3-ylphosphonate；3-diethoxyphosphoryloxan-2-one
• CAS: 122593-65-1
• 化学式: C₉H₁₇O₅P
• 分子量: 236.205
• InChiKey: WYXBTGCFOPOZLW-UHFFFAOYSA-N

物化性质

• 沸点：
  379.9±31.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  α-(diethoxyphosphinyl)-δ-valerolactone 在 samarium diiodide 、 18-冠醚-6 、 potassium carbonate 、 叔丁醇 作用下， 以 四氢呋喃 为溶剂， 反应 22.5h， 生成 (1RS,5SR)-1-benzyl-4-(3-hydroxypropyl)-2-oxabicyclo[3.2.0]heptan-3-one
  参考文献：
  名称：

  通过酒精助溶剂的简单变化在新型sa（II）介导的环化之间进行切换。

  摘要：

  根据反应中使用的醇助溶剂，γ-不饱和酮会经历由碘化sa（II）介导的两个非常不同的立体选择性环化反应。只需将醇助溶剂从甲醇更改为叔丁醇，即可在前所未有的羟醛螺环化和新型环丁醇形成工艺之间进行切换。[反应：看文字]

  DOI：

  10.1021/ol0358399
• 作为产物：
  描述：

  Phosphoric acid 5,6-dihydro-4H-pyran-2-yl ester diethyl ester 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 α-(diethoxyphosphinyl)-δ-valerolactone
  参考文献：
  名称：

  Synthesis of .alpha.-phosphono lactones and esters through a vinyl phosphate-phosphonate rearrangement

  摘要：

  DOI：

  10.1021/jo00281a012

文献信息

• NON-AQUEOUS LIQUID ELECTROLYTE, ELECTRICITY STORAGE DEVICE USING SAME, AND PHOSPHORUS COMPOUND USED THEREIN
  申请人：UBE INDUSTRIES, LTD.

  公开号：US20170275311A1

  公开（公告）日：2017-09-28

  The present invention is concerned with a nonaqueous electrolytic solution having an electrolyte salt dissolved in a nonaqueous solvent, the nonaqueous electrolytic solution containing a compound represented by the following general formula (X), in which a polar group (X) is bound to a phosphorus atom (P), and capable of improving electrochemical characteristics in a broad temperature range; an energy storage device using the same; and a novel compound. In the formula, R 10 and R 20 are each independently an organic group selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms, or a lithium atom; and X is a polar group (i) containing a —C(═O) group, a —P(═O) group, or an —S(═O) 2 group, a polar group (ii) containing a —CN group or an alkyl group having 1 to 6 carbon atoms, in which a part of hydrogen atoms is substituted with a fluorine atom, or a 4- to 7-membered ring polar group (iii) containing a —C(═O)—O— group or a —C(═O)—N— group, provided that when X is a 4- to 7-membered ring polar group (iii) containing a —C(═O)—N— group, at least one of R 10 and R 20 is a lithium atom.

  本发明涉及一种非水电解质溶液，其中电解质盐溶解在非水溶剂中，该非水电解质溶液含有以下通式（X）所代表的化合物，其中极性基（X）与磷原子（P）结合，并能够改善广泛温度范围内的电化学特性；使用该非水电解质溶液的储能装置；以及一种新化合物。在该公式中，R10和R20分别独立地是从包括具有1至8个碳原子的烷基基团、具有2至6个碳原子的烯基基团、具有3至6个碳原子的炔基基团和具有6至12个碳原子的芳基基团或锂原子中选择的有机基团；X是一个极性基（i），其中包含一个—C(═O)基团、一个—P(═O)基团或一个—S(═O)2基团，一个极性基（ii），其中包含一个—CN基团或一个具有1至6个碳原子的烷基基团，其中部分氢原子被氟原子取代，或一个4至7环极性基（iii），其中包含一个—C(═O)—O—基团或一个—C(═O)—N—基团，但当X是一个包含一个—C(═O)—N—基团的4至7环极性基（iii）时，至少一个R10和R20是锂原子。
• Copper-Catalyzed Asymmetric Synthesis of Tertiary α-Hydroxy Phosphonic Acid Derivatives with In Situ Generated Nitrosocarbonyl Compounds as the Oxygen Source
  作者：Biplab Maji、Hisashi Yamamoto

  DOI：10.1002/anie.201408893

  日期：2014.12.22

  α‐Hydroxy phosphonic acids and their derivatives are highly bioactive structural motifs. It is now reported that these compounds can be accessed through the copper‐catalyzed direct α‐oxidation of β‐ketophosphonates using in situ generated nitrosocarbonyl compounds as an electrophilic oxygen source. These reactions proceeded in high yields (up to 95 %) and enantioselectivities (up to >99 % ee) for both

  α-羟基膦酸及其衍生物是具有高生物活性的结构基序。据报道，这些化合物可通过原位生成的亚硝基羰基化合物作为亲电子氧源，通过铜催化的β-酮膦酸酯的直接α-氧化而获得。对于环状和非环状底物，这些反应均以高产率（最高95％）和对映选择性（最高> 99％ee）进行。该方法还用于合成α，β-二羟基膦酸酯和β-氨基-α-羟基膦酸酯。
• Synthesis of β-Hydroxy-α,α-disubstituted Amino Acids through the Orthoamide-Type Overman Rearrangement of an α,β-Unsaturated Ester and Stereodivergent Intramolecular S_N2′ Reaction: Development and Application to the Total Synthesis of Sphingofungin F
  作者：Tomoya Sugai、Shunme Usui、Shun Tsuzaki、Hiroki Oishi、Daichi Yasushima、Shoko Hisada、Takahiro Fukuyasu、Takeshi Oishi、Takaaki Sato、Noritaka Chida

  DOI：10.1246/bcsj.20170408

  日期：2018.4.15

  β-hydroxy-α,α-disubstituted amino acid derivatives from cyclic orthoamide is reported. The first step is the orthoamide-type Overman rearrangement of an α,β-unsaturated ester to give a sterically hindered α,α-disubstituted amidoester. The α,β-unsaturated ester is known to be a challenging substrate in the conventional Overman rearrangement due to the competitive aza-Michael reaction. However, suppression

  报道了从环状原酰胺中两步合成 β-羟基-α,α-二取代氨基酸衍生物的发展。第一步是 α,β-不饱和酯的邻酰胺型 Overman 重排，得到位阻的 α,α-二取代酰胺酯。由于竞争性 aza-Michael 反应，已知 α,β-不饱和酯是常规 Overman 重排中具有挑战性的底物。然而，aza-Michael 反应的抑制是通过两个因素实现的：1) 反应温度高，和 2) α-位有烷基取代基。第二步是立体发散分子内SN2'反应，用于在β-位安装羟基。通过简单地改变反应条件，无论是同型还是反型 SN2' 反应都是可能的。
• Total Synthesis of Sphingofungin F by Orthoamide-Type Overman Rearrangement of an Unsaturated Ester
  作者：Shun Tsuzaki、Shunme Usui、Hiroki Oishi、Daichi Yasushima、Takahiro Fukuyasu、Takeshi Oishi、Takaaki Sato、Noritaka Chida

  DOI：10.1021/acs.orglett.5b00475

  日期：2015.4.3

  through the Overman rearrangement of an unsaturated ester, which is known to be an unsuitable substrate under standard conditions due to the competitive aza-Michael reaction, is described. The developed conditions enabled the ester to be compatible with the original Overman rearrangement, providing quick access to α,α-disubstituted amino acids by minimizing extra protecting group manipulations and redox

  描述了通过不饱和酯的Overman重排进行的鞘氨醇单糖F的全合成，由于竞争性的氮杂-迈克尔反应，在标准条件下，该不饱和酯被认为是不合适的底物。改进的条件使该酯与原始的Overman重排相容，并通过最大限度地减少额外的保护基操纵和氧化还原反应，提供了对α，α-二取代氨基酸的快速访问。
• Temperature Effects on Stereocontrol in the Horner−Wadsworth−Emmons Condensation of α-Phosphono Lactones
  作者：Jose S. Yu、David F. Wiemer

  DOI：10.1021/jo070722+

  日期：2007.8.1

  The Horner−Wadsworth−Emmons condensation of some α-phosphono lactones has been examined for conditions that impact product stereochemistry. The temperature employed to quench the reaction was found to be a major factor. For example, after the diethyl phosphonate derivative of γ-butyrolactone was treated with potassium hexamethyldisilazane, 18-crown-6, and propionaldehyde at −78 °C in THF, an aliquot

  对某些α-膦酰基内酯的霍纳-沃兹沃思-埃蒙斯缩合反应进行了影响产物立体化学的条件研究。发现用于淬灭反应的温度是主要因素。例如，将γ-丁内酯的二乙基膦酸酯衍生物在THF中在-78°C下用六甲基二硅氮烷钾，18-crown-6和丙醛处理后，等分试样转移到约30°C的烧瓶中，几乎得到Z -烯烃产物，尽管允许其在数小时内升温至室温，却非常有利于E-烯烃。