1-(N,N-Diethylcarbamoyloxy)-2,2-difluoro-1-(tributylstannyl)ethene

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-(N,N-Diethylcarbamoyloxy)-2,2-difluoro-1-(tributylstannyl)ethene
• 英文别名: 2,2-difluoro-1-(N,N-diethylcarbamoyloxy)-1-tributylstannyl ethene；1-(N,N-diethylcarbamoyloxy)-2,2-difluoroethenyl tributylstannane；Diethylcarbamic acid 1-(tributylstannyl)-2,2-difluorovinyl ester
• 化学式: C₁₉H₃₇F₂NO₂Sn
• 分子量: 468.215
• InChiKey: AODKBYTVDSNSAO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.96
• 重原子数：
  25
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(N,N-Diethylcarbamoyloxy)-2,2-difluoro-1-(tributylstannyl)ethene 在 正丁基锂 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.75h， 生成 2-[1'-(N,N-diethylcarbamoyloxy)-2',2'-difluoroethenyl]-cyclohexan-1-one
  参考文献：
  名称：

  Syntheses of selectively fluorinated cyclodecenones: the first deployment of the neutral oxy-Cope rearrangement in organofluorine chemistry

  摘要：

  使用金属卤代烯打开环氧化物的收率为中等到良好。得到的均烯丙基醇经过 Swern 氧化反应得到三种 γ,γ-二氟化 β,γ-烯酮，它们与乙烯基锂、2-二硫代-2H-二氢吡喃或另一种金属化卤代烃反应，得到不同稳定度的取代反式-1,2-二乙烯基环己醇。这些中间体在 Ace® 管中的二甲苯中加热时会发生中性热氧-科普重排。第一次生成的烯醇在不损失 HF 的情况下发生酮化，从而得到一系列环癸烯酮，收率从中等到良好；X 射线晶体学被广泛用于产品特征描述。与 1,2-二乙烯基环己醇的顺式/反式混合物相比，所有底物的重排速度都更快。

  DOI：

  10.1039/b311261f

文献信息

• Highly-functionalised difluorinated (hydroxymethyl)conduritol analogues via the Diels–Alder reactions of a difluorinated dienophile
  作者：Andrea Arany、Patrick J. Crowley、John Fawcett、Michael B. Hursthouse、Benson M. Kariuki、Mark E. Light、Andrew C. Moralee、Jonathan M. Percy、Vittoria Salafia

  DOI：10.1039/b314314g

  日期：——

  A difluorodienophile, synthesised using a Stille coupling reaction underwent tin(IV)-catalysed cycloaddition with three furans to afford oxa[2.2.1]bicycloheptenes in good yield. Reduction of ester and carbamate carbonyl groups and diol protection as the acetonide set the stage for palladium-catalysed hydrostannylation in two cases. Treatment of the stannanes with methyllithium triggered ring-opening to afford highly-functionalised difluorinated cyclohexenols which could be deprotected to afford (hydroxymethyl)conduritol analogues.

  一种二氟二烯亲核体，通过Stille偶联反应合成，经过锡(IV)催化的环加成与三种呋喃反应，良好产率地生成了oxa[2.2.1]双环庚烯。酯和氨基甲酸酯的酮基还原以及二醇保护为在两种情况下进行的钯催化氢锡化反应奠定了基础。将锡烷与甲基锂处理引发开环，生成高度功能化的二氟化环己烯醇，这些化合物可以去保护，得到(hydroxymethyl)conduritol类似物。
• Applying asymmetric dihydroxylation to the synthesis of difluorinated carbohydrate analogues: a 1,1-difluoro-1-deoxy-d-xylulose
  作者：Liam R. Cox、Gareth A. DeBoos、Jeremy J. Fullbrook、Jonathan M. Percy、Neil Spencer

  DOI：10.1016/j.tetasy.2004.11.017

  日期：2005.1

  AD conditions. A number of issues were raised including generally low reactivity of simple 1,3-butadienes, and useful reactivity of certain 1,4- and substituted 1,3-pentadienes. Though the basic conditions used for the AD resulted in the decomposition of certain diol products, enol acetal chemistry allowed the asymmetric synthesis of a difluorinated analogue of a deoxyxylulose.

  现成的二氟烯醇碘化物和锡烷分别与链烯基锡和碘化物进行钯催化的偶联反应，得到一组二氟的1,3-二烯和1,4-二烯的试验样品，然后将其暴露于AD条件下。提出了许多问题，包括简单的1,3-丁二烯的反应性通常较低，以及某些1,4-和取代的1,3-戊二烯的有用的反应性。尽管用于AD的基本条件导致某些二醇产物的分解，但是烯醇缩醛化学允许脱氧木酮糖的二氟类似物的不对称合成。
• A practical, versatile difluorovinylcopper reagent
  作者：P.J. Crowley、J.A. Howarth、W.M. Owton、J.M. Percy、K. Stansfield

  DOI：10.1016/0040-4039(96)01179-3

  日期：1996.8

  Transmetallation of an α-lithio-β,β-difluoroenol carbamate with a CuX3Li2 (2LiCl.Cul) produced a vinylcopper reagent that was thermally stable and reacted with activated haloalkanes and acid chlorides in moderate to high yield, extending considerably the scope of building block chemistry available from trifluoroethanol.

  α-硫代-β，β-二氟烯醇氨基甲酸酯与CuX 3 Li 2（2LiCl.Cul）的金属转移产生了乙烯基铜试剂，该试剂具有热稳定性，并与活化的卤代烷烃和酰氯反应，具有中等至高收率，从而大大扩展了应用范围可从三氟乙醇中获得的基础化学原料。
• Suzuki–Miyaura Coupling Reactions of Iodo(difluoroenol) Derivatives, Fluorinated Building Blocks Accessible at Near-Ambient Temperatures
  作者：Peter G. Wilson、Jonathan M. Percy、Joanna M. Redmond、Adam W. McCarter

  DOI：10.1021/jo3011705

  日期：2012.8.3

  A recently developed method for the near-ambient generation of difluorovinylzinc reagents has facilitated the preparation of 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro1-iodoethene and 2,2-difluoro-1-iodo-1-(2'-methoxyethoxymethoxy)ethene. The utility of these reagents has been investigated in Suzuki-Miyaura couplings with a range of potassium trifluoroborate coupling partners, with the scope of successful couplings proving wide. Deiodinated species appeared as significant side products, but a solvent change from i-PrOH to t-BuOH suppressed the pathway to these species and improved coupling yields.
• New fluorine-containing building blocks from trifluoroethanol. 2.
  作者：Judith A. Howarth、W. Martin Owton、Jonathan M. Percy、Michael H. Rock

  DOI：10.1016/0040-4020(95)00588-y

  日期：1995.9

  A new fluorine containing acyl anion equivalent 1,1 -difluoro-2-lithio-2-[(N,N-diethylcarbamato)-ethene 9 has been prepared and trapped with a number of electrophiles in good yields. Transacylation of the first formed lithium alkoxides releases a difluoroenolate, affording difluoromethylketones upon work-up.