bis(2,2,2-trifluoroethyl)(methoxy)carbonylmethylphosphonate | 115384-91-3

• 分子结构分类: 有机化合物 - 有机磷化合物 - 磷芥子化合物
• 英文名称: bis(2,2,2-trifluoroethyl)(methoxy)carbonylmethylphosphonate
• 英文别名: methyl P,P-bis(2,2,2-trifluoroethyl)phosphonoacetate；MeO2CCH2P(O)(OCH2CF3)2；[Bis(2,2,2-trifluoroethyl)phosphinyl]acetic acid methyl ester；methyl 2-[bis(2,2,2-trifluoroethyl)phosphoryl]acetate
• CAS: 115384-91-3
• 化学式: C₇H₉F₆O₃P
• 分子量: 286.111
• InChiKey: DYOZLTRMPIXBKM-UHFFFAOYSA-N

物化性质

• 沸点：
  276.4±40.0 °C(Predicted)
• 密度：
  1.399±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  5-oxohexanal 、 bis(2,2,2-trifluoroethyl)(methoxy)carbonylmethylphosphonate 在 18-冠醚-6 、 乙腈 作用下， 以 甲苯 为溶剂， 反应 0.5h， 以80%的产率得到methyl Z-7-oxooct-2-enoate
  参考文献：
  名称：

  Intramolecular Michael Addition of N- and O-Centred Nucleophiles to Tethered Acrylates. The Role of Double-Bond Geometry in Controlling the Diastereo- selectivity of Cyclizations Leading to 2,6-Disubstituted Tetrahydropyrans and Piperidines.

  摘要：

  羟基丙烯酸酯 E-(5)的氧阴离子 发生顺畅的分子内迈克尔加成反应，得到反式-2,6-二取代的四氢吡喃（7 反式-2,6-二取代的四氢吡喃（7）作为主要反应产物。 反应的主要产物。相反，从异构体 Z-(5) 环化生成 顺式-2,6-二取代的四氢吡喃（6）为主要反应产物。 产品。这种化学反应已经扩展到对映体选择性合成 (+)-(6) 的对映体选择性合成。 酸 (+)-(2) 的正式全合成。 (Viverra civetta)腺分泌物的一种成分。酮基丙烯酸酯的还原胺化反应 (12) 发生还原胺化反应，生成中间胺，并在原位环化、 在原位环化，生成 顺式-2,6-二取代哌啶 (26)。类似的 处理化合物 (13) 得到异构体 反式-2,6-二取代哌啶（27）作为唯一的 反应产物。有人提出了过渡态结构来解释 在所有环化反应中观察到的非对映选择性。

  DOI：

  10.1071/c97173

文献信息

• Application of Oxazolidinone α-Fluoro Amide Chiral Building Blocks in the Asymmetric Synthesis of Fluorinated Carbohydrates: 2-Deoxy-2-fluoropentoses
  作者：Franklin A Davis、Hongyan Qi、Gajendran Sundarababu

  DOI：10.1016/s0040-4020(00)00444-0

  日期：2000.7

  Deconjugative electrophilic fluorination of the lithium dienolate of Z-α,β-unsaturated imide (+)-9 with N-fluorobenzenesulfonimide (NFSi) afforded the E-β,γ-unsaturated α-fluoro imide (+)-10 as a single diastereoisomer. Dihydroxylation resulted in the formation of 2-fluoro-2-deoxy-γ-xylonic and -lyxonic lactones, 12a and 12b, respectively. Reduction and deprotection of the lactones afforded 2-deox

  Z -α，β-不饱和酰亚胺（+）- 9的二烯酸锂与N-氟苯磺酰亚胺（NFSi）的去共轭亲电氟化得到E -β，γ-不饱和α-氟酰亚胺（+）- 10作为单一非对映异构体。二羟基化分别形成2-氟-2-脱氧-γ-木糖基内酯和-Lyxonic内酯12a和12b。内酯的还原和脱保护得到2-脱氧-2-氟-木糖基-吡喃糖（15）和2-脱氧-2-氟-木糖基-1-吡喃糖（17）。
• New coumarins from Harbouria trachypleura: isolation and synthesis
  作者：Nathan R Guz、Peter Lorenz、Frank R Stermitz

  DOI：10.1016/s0040-4039(01)01355-7

  日期：2001.9

  (+)-epoxysuberosin, and two new coumarins (+)-trachypleuranin-A and (±)-trachypleuranin-B, were isolated from the methanol extract of Harbouria trachypleura. An efficient five-step asymmetric synthesis of (+)-trachypleuranin-A was performed using a sequential [3,3] Claisen–Cope rearrangement and a Shi asymmetric epoxidation. (±)-Trachypleuranin-B, a chlorinated coumarin, was synthesized from (±)-epoxysuberosin

  分离出两种已知的呋喃香豆素，（+）-氧哌丁宁和（+）-萨克萨林，两种已知的香豆素，伞形酮和（+）-环氧亚油精，以及两种新的香豆素，（+）-trachypleuranin-A和（±）-trachypleuranin-B。从夏威夷夏威夷藻的甲醇提取物中提取。使用顺序的[3,3] Claisen-Cope重排和Shi不对称环氧化，进行了有效的五步（+）-trachypleuranin-A不对称合成。（±）-Trachypleuranin-B，一种氯代香豆素，是由（±）-环氧亚油精合成的。
• Biphilic Organophosphorus Catalysis: Regioselective Reductive Transposition of Allylic Bromides via P^III/P^VRedox Cycling
  作者：Kyle D. Reichl、Nicole L. Dunn、Nicholas J. Fastuca、Alexander T. Radosevich

  DOI：10.1021/jacs.5b01899

  日期：2015.4.29

  We report that a regioselective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosphorus (phosphetane) catalyst. Spectroscopic, evidence supports the formation of a penta:coordinate (sigma(5)-P) hydridophosphorane as a key reactive intermediate. Kinetics experiments and computational modeling are consistent with a unimolecular docomposition of the sigma(5)-P hydridophosphorane via a conceited cyclic transition,structure that delivers the observed allylic transposition and completes a novel P-III/P-V redox Catalytic cycle. These results broaden the growing repertoire., of reactions catalyzed within the P-III/P-V redox couple and suggest additional opportunities for organophosphorus,catalysis in a biphilic mode.
• Stereoselective first total synthesis of (R)-rugulactone
  作者：D. Kumar Reddy、V. Shekhar、T. Srikhanth Reddy、S. Purushotham Reddy、Y. Venkateswarlu

  DOI：10.1016/j.tetasy.2009.09.016

  日期：2009.10

  A simple and highly efficient stereoselective synthetic route has been developed for the synthesis of (R)-rugulactone, a 6-arylalkyl-5,6-dihydro-2H-pyran-2-one, from readily available substrates such as 1,3-propanediol and 3-phenyl-1-propanal employing Keck's asymmetric allylation and cross metathesis as key steps. (C) 2009 Elsevier Ltd. All rights reserved.
• Synthesis and transannular diels-alder reaction of a trans-cis-cis 13-membered macrocyclic trienono
  作者：Kurt Baettig、Anne Marinier、Rita Pitteloud、Pierre Deslongchamps

  DOI：10.1016/s0040-4039(00)96700-5

  日期：1987.1