lithium di-tert-butylcyanocuprate

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: lithium di-tert-butylcyanocuprate
• 化学式: CCuN*2C₄H₉Li
• 分子量: 217.677
• InChiKey: JSWGKATYMBEJLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.33
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-叔丁基丙二酰二氯 、 lithium di-tert-butylcyanocuprate 生成 tert-butyl-(2,2-dimethyl-propionyl)-ketene
  参考文献：
  名称：

  Direct observation of .alpha.-oxo ketenes from the photolysis of .alpha.-diazo .beta.-diketones

  摘要：

  Monitoring by IR spectroscopy of the broad-band irradiation of the symmetrically substituted 2-diazo-cyclohexane-1,3-dione (I 1), 3-diazopentane-2,4-dione (19), and 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione (24) in Ar matrices at 12 K showed the formation of 2-carbonylcyclopentanone (s-Z-12), acetyl(methyl)ketene (s-E-20), and tert-butyl(pivaloyl)ketene (s-E-25), respectively, in less than 10 min. On increasing the photolysis time to >3 h, the alpha-oxo ketenes 12,20, and 25 decarbonylated to the corresponding oxocarbenes which underwent Wolff rearrangement to carbonylcyclobutane (15), dimethylketene (23), and di-tert-butylketene (28), respectively. The reaction of 2-carbonylcyclopentanone (12) with CH3OH was monitored by IR spectroscopy. Thus, it was found that the reaction started at ca. 100 K and was essentially complete at 140 K, involving the initial formation of the enol form (9) of methyl 2-oxocyclopentanecarboxylate.

  DOI：

  10.1021/jo00044a019

文献信息

• Regio- and Stereocontrol in the Reactions of α-Halo-β,γ-enoates and α-<i>O</i>-Phosphono-β,γ-enenitriles with Organocuprates
  作者：R. Karl Dieter、Alfredo Picado

  DOI：10.1021/jo502111c

  日期：2014.11.21

  The reactions of (Z)- and (E)-ethyl 2-chloro-3-octenoate (4a and 17) and (E)- and (Z)-diethyl (1-cyano-2-heptenyl)phosphate (21a and 21b) with organocuprates were investigated as potential substrates for preparing γ-substituted α,β-enoates and enenitriles. In these copper-mediated allylic substitution reactions, the Z-isomer 4a displayed complete regio- and stereoselectivity (i.e., E:Z), while the

  （Z）-和（E）-2-氯-3-辛烯酸乙酯（4a和17）与（E）-和（Z）-二乙基（1-氰基-2-庚烯基）磷酸酯（21a和21b）的反应）以有机铜酸盐作为制备γ-取代的α，β-烯酸酯和烯类化合物的潜在底物进行了研究。在这些铜介导的烯丙基取代反应中，Z异构体4a表现出完全的区域和立体选择性（即E：Z），而对E异构体的区域和立体选择性17随溶剂，铜酸盐试剂，可转移配体和铜酸盐抗衡离子而变化（例如Li + vs MgX +）。在Et 2 O中使用17和n BuCuCNLi可以实现极好的选择性。发现烯丙基氰基磷酸酯的反应选择性比以前报道的有所提高的条件。进行了一系列相对速率和竞争实验，并根据对铜酸盐介导的烯丙基取代反应的当前机械理解，合理化了每个系统的区域选择性和立体选择性。
• Krause, Norbert, Chemische Berichte, 1991, vol. 124, # 11, p. 2633 - 2636
  作者：Krause, Norbert

  DOI：——

  日期：——
• Enantioselective synthesis of (1S,2S)-1,2-di-tert-butyl and (1R,2R)-1,2-di-(1-adamantyl)ethylenediamines
  作者：Alaa A.-M. Abdel-Aziz、Serry A.A. El Bialy、Fatma E. Goda、Takehisa Kunieda

  DOI：10.1016/j.tetlet.2004.08.164

  日期：2004.10

  An enantioselective synthesis of sterically congested 1,2-di-tert-butyl and 1,2-di-(1-adamantyl)ethylenediamines has been developed. Thus, diastereomerically pure trans-1-apocamphanecarbonyl-4,5-dimethoxy-2-imidazolidinones 6 and 7 were successfully prepared by optical resolution of (+/-)-trans-4,5-dimethoxy-2-imidazolidinone using apocamphanecarbonyl chloride (MAC-Cl) followed by stereospecific and stepwise substitution of the dimethoxyl groups using tert-butyl or 1-adamantyl cuprates to provide (4S,5S)-4,5-di-tert-butyl and (4R,5R)-4,5-di-(1-adamantyl)-2-imidazolidinones 12 and 15, respectively. Furthermore, N-acetyl 4,5-di-tert-butyl and 4,5-di-(1-adamantyl)-2-imidazolidinones 16a,b were enantioselectively deacetylated using a catalytic oxazaborolidine system to provide enantiopure 1-p-tolylsulfonyl-4,5-di-tert-butyl-2-imidazolidinones 12 and 19 and 1-p-tolylsulfonyl-4,5-di-(1-adamantyl)-2-imidazolidinones 18 and 20, respectively. Finally, N-p-tolylsulfonyl-2-imidazolidinones 12 and 15 were treated with 30equiv of Ba(OH)(2.)8H(2)O to achieve ring cleavage and to provide (1S,2S)-1,2-di-tert-butylethylenediamine 3 and (1R,2R)-1,2-di(1-adamantyl)ethylenediamine 4. (C) 2004 Elsevier Ltd. All rights reserved.
• AUVRAY, P.;KNOCHEL, P.;NORMANT, J. F., TETRAHEDRON, 44,(1987) N 19, C. 6095-6106
  作者：AUVRAY, P.、KNOCHEL, P.、NORMANT, J. F.

  DOI：——

  日期：——
• Direct observation of .alpha.-oxo ketenes from the photolysis of .alpha.-diazo .beta.-diketones
  作者：Regis Leung-Toung、Curt Wentrup

  DOI：10.1021/jo00044a019

  日期：1992.8

  Monitoring by IR spectroscopy of the broad-band irradiation of the symmetrically substituted 2-diazo-cyclohexane-1,3-dione (I 1), 3-diazopentane-2,4-dione (19), and 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione (24) in Ar matrices at 12 K showed the formation of 2-carbonylcyclopentanone (s-Z-12), acetyl(methyl)ketene (s-E-20), and tert-butyl(pivaloyl)ketene (s-E-25), respectively, in less than 10 min. On increasing the photolysis time to >3 h, the alpha-oxo ketenes 12,20, and 25 decarbonylated to the corresponding oxocarbenes which underwent Wolff rearrangement to carbonylcyclobutane (15), dimethylketene (23), and di-tert-butylketene (28), respectively. The reaction of 2-carbonylcyclopentanone (12) with CH3OH was monitored by IR spectroscopy. Thus, it was found that the reaction started at ca. 100 K and was essentially complete at 140 K, involving the initial formation of the enol form (9) of methyl 2-oxocyclopentanecarboxylate.