2,3-二甲基丁-1-烯-1-酮 | 59005-30-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,3-二甲基丁-1-烯-1-酮
• 英文名称: isopropyl methyl ketene
• 英文别名: isopropylmethylketene；1-Buten-1-one, 2,3-dimethyl-
• CAS: 59005-30-0
• 化学式: C₆H₁₀O
• 分子量: 98.1448
• InChiKey: NMGZDMNQLYMUAB-UHFFFAOYSA-N

物化性质

• 沸点：
  83.6±7.0 °C(Predicted)
• 密度：
  0.793±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,3-二甲基丁-1-烯-1-酮 生成 2,4-Dimethyl-2,4-di(propan-2-yl)cyclobutane-1,3-dione
  参考文献：
  名称：

  DEHMLOW E. V.; PICKARDT J.; SLOPIANKA M.; FASTABEND U.; DRECHSLER K.; SOU+, LIEBIGS ANN. CHEM.,(1987) N 4, 377-379

  摘要：

  DOI：
• 作为产物：
  描述：

  2-bromo-2,3-dimethylbutanoyl chloride 在 锌 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 2,3-二甲基丁-1-烯-1-酮
  参考文献：
  名称：

  通过亲核试剂催化双取代烯酮与醛的[2 + 2]环加成反应，不对称合成高度取代的β-内酯。

  摘要：

  DOI：

  10.1002/anie.200460698

文献信息

• Phosphine-Catalyzed Diastereoselective Synthesis of β-Lactones from Disubstituted Ketenes and α-Chiral Oxyaldehydes
  作者：Mukulesh Mondal、Shi Chen、Nabil Othman、Kraig A. Wheeler、Nessan J. Kerrigan

  DOI：10.1021/acs.joc.5b00869

  日期：2015.6.5

  In this article we describe a catalytic procedure for the diastereoselective synthesis of β-lactones bearing two stereogenic centers, from disubstituted ketenes and α-chiral oxyaldehydes. Tri-n-butylphosphine was found to be the optimal catalyst in terms of effecting both good yield and diastereoselectivity (dr from 3:1 to 32:1 for 8 examples) in β-lactone formation. The major isomer of the β-lactone

  在本文中，我们描述了一种催化方法，用于从双取代的烯酮和α-手性乙醛中非立体选择性合成带有两个立体生成中心的β-内酯。三Ñ丁基膦被发现是在（3 DR 1 8实施例：1〜32）都实现良好的收率非对映选择性和方面的最佳催化剂在β内酯的形成。在β内酯产品的主要异构体被确定为是反非对映体，它的形成是由极性Felkin-映模型合理化。通过31 P NMR光谱的反应监测表明了烯醇盐中间体参与反应机理。（+）-peloruside A合成子的短合成证明了该方法的实用性。
• Phosphine-catalyzed synthesis of β-lactones from ketenes and chiral β-oxyaldehydes
  作者：Shi Chen、Mukulesh Mondal、Matthew P. Adams、Kraig A. Wheeler、Nessan J. Kerrigan

  DOI：10.1016/j.tetlet.2015.09.141

  日期：2015.11

  catalytic procedure for the diastereoselective synthesis of β-lactones bearing up to three stereogenic centers, from disubstituted ketenes and chiral β-oxyaldehydes. Tri-n-butylphosphine was determined to be the best catalyst with yields of up to 95% and moderate to good diastereoselectivity (dr up to 4:1) obtained in the formation of highly substituted β-lactones.

  在这封信中，我们描述了一种由双取代的烯酮和手性的β-乙氧基醛组成的非对映选择性合成β-内酯的催化程序，该β-内酯最多可容纳三个立体中心。三Ñ丁基膦被确定为具有高达95％的产率的最佳催化剂和中度至良好的非对映选择性（DR高达4：1）在高度取代的β-内酯的形成而获得。
• Asymmetric synthesis of enantioenriched α-allyl esters through Pd(BINAPHANE)-catalysed allylation of disubstituted ketenes
  作者：Ahmad A. Ibrahim、Stephen C. J. O’Reilly、Margot Bottarel、Nessan J. Kerrigan

  DOI：10.1039/d4cc00057a

  日期：2024.3.19

  Pd2dba3·CHCl3 (2.5 mol%)-BINAPHANE (5 mol%) was used to promote the first catalytic enantioselective allylation of disubstituted ketenes to give α-allyl esters. The ester products were formed in good to excellent yields (61–93% yield for 13 examples, 16 examples in all), with moderate to good enantioselectivity (68–80% ee for 7 examples).

  Pd 2 dba 3 ·CHCl 3 (2.5 mol%)-BINAPHANE (5 mol%)用于促进双取代烯酮的首次催化对映选择性烯丙基化反应生成α-烯丙酯。酯产物的产率从良好到优异（13 个实例的产率为 61-93%，总共 16 个实例），具有中等至良好的对映选择性（7 个实例为 68-80% ee）。
• BINAPHANE-Catalyzed Asymmetric Synthesis of <i>trans</i>-β-Lactams from Disubstituted Ketenes and <i>N</i>-Tosyl Arylimines
  作者：Shi Chen、Eric C. Salo、Kraig A. Wheeler、Nessan J. Kerrigan

  DOI：10.1021/ol3003783

  日期：2012.4.6

  The development of a BINAPHANE-catalyzed formal [2 + 2]-cycloaddition of disubstituted ketenes and inexpensive N-tosyl arylimines that provides access to a variety of highly substituted beta-lactams (16 examples) is described. The BINAPHANE catalytic system displays moderate to excellent enantioselectivity (up to 98% ee) and high diastereoselectivity in most cases, favoring formation of the trans-diastereomer (13 examples with >= 90:10).
• Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl Fluorides via the α-Fluorination of Ketenes: Synthetic and Mechanistic Studies
  作者：Sarah Yunmi Lee、Stefan Neufeind、Gregory C. Fu

  DOI：10.1021/ja5044209

  日期：2014.6.25

  The catalytic asymmetric synthesis of alkyl fluorides, particularly alpha-fluorocarbonyl compounds, has been the focus of substantial effort in recent years. While significant progress has been described in the formation of enantioenriched secondary alkyl fluorides, advances in the generation of tertiary alkyl fluorides have been more limited. Here, we describe a method for the catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C6F5ONa to furnish tertiary alpha-fluoroesters. Mechanistic studies are consistent with the hypothesis that the addition of an external nucleophile (C6F5ONa) is critical for turnover, releasing the catalyst (PPY*) from an N-acylated intermediate. The available data can be explained by a reaction pathway wherein the enantioselectivity is determined in the turnover-limiting transfer of fluorine from NFSI to a chiral enolate derived from the addition of PPY* to the ketene. The structure and the reactivity of the product of this proposed elementary step, an alpha-fluoro-N-acylpyridinium salt, have been examined.