lithium diphenylcuprate | 7237-89-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: lithium diphenylcuprate
• CAS: 7237-89-0
• 化学式: C₆H₅Cu*C₆H₅Li
• 分子量: 224.698
• InChiKey: LIHCSPFJNOOKIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.59
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (E)-dimethyl hex-2-enedioate 、 lithium diphenylcuprate 以 乙醚 为溶剂， 反应 0.5h， 以66%的产率得到2-氧代-5-苯基环戊烷-1-羧酸甲酯
  参考文献：
  名称：

  A regiospecific, convergent route to 2,3-disubstituted cyclopentanones

  摘要：

  DOI：

  10.1021/jo00174a043

文献信息

• Chlorosilane-accelerated conjugate addition of catalytic and stoichiometric organocopper reagents
  作者：Satoshi Matsuzawa、Yoshiaki Horiguchi、Eiichi Nakamura、Isao Kuwajima

  DOI：10.1016/0040-4020(89)80064-x

  日期：1989.1

  Trialkylsilyl chlorides, particularly in combination with hexamethylphosphoramide or 4-dimethylaminopyridine, dramatically accelerates the conjugate addition of catalytic and stoichiometric organocopper reagents onto enones, enals, and enoates, in which very high degrees of stereo- and chemoselectivities were observed.

  三烷基甲硅烷基氯化物，特别是与六甲基磷酰胺或4-二甲基氨基吡啶组合，可显着加速催化和化学计量的有机铜试剂在烯酮，烯醛和烯酸酯上的共轭加成，其中观察到很高的立体和化学选择性。
• A Michael Addition and Peterson Olefination Sequence Using 1-Silylethenyl Sulfides and Sulfoxide
  作者：Shuji Kanemasa、Hiroshi Kobayashi、Junji Tanaka、Otohiko Tsuge

  DOI：10.1246/bcsj.61.3957

  日期：1988.11

  Reaction of organolithiums with a 1-(trimethylsilyl)ethenyl sulfide produces 1,2-bis(trimethylsilyl)cyclopropanes, while use of 1-silylethenyl sulfides bearing a bulkier silyl moiety results in exclusive formation of the corresponding Michael adduct anions which are then quenched with aldehydes to give vinyl sulfides. On the contrary, a 1-(trimethylsilyl)ethenyl sulfoxide undergoes smooth Michael addition with a variety of organo-metallics and the resulting carbanion intermediates can be quenched with aldehydes to produce vinyl sulfoxides. Scope and limitations of these sequential reactions are discussed.

  有机锂与 1-(三甲基硅烷基)乙烯基硫醚反应可生成 1,2-双(三甲基硅烷基)环丙烷，而使用带有较多硅基的 1-硅烷基乙烯基硫醚则只能形成相应的迈克尔加成阴离子，然后用醛淬灭，生成乙烯基硫化物。相反，1-(三甲基硅烷基)乙烯基亚砜会与多种有机金属发生顺畅的迈克尔加成反应，生成的碳阴离子中间体可以用醛淬灭，生成乙烯基硫醚。本文讨论了这些连续反应的范围和局限性。
• Some unusual aspect aspects of organocopper chemistry: lithium organocuprate reaction with some neopentylic p-tosylate esters
  作者：Gary H. Posner、Kevin A. Babiak

  DOI：10.1016/s0022-328x(00)92356-8

  日期：1979.9

  Diphenylcopperlithium and dimethylcopperlithium react differently with the same primary neopentylic tosylate ester. Several secondary neopentylic tosylates react with organocopperlithium reagents to give olefins via a concerted anti-1,2-dehydrosulfonation. When anti-elimination is not possible, skeletal rearrangement occurs.

  二苯基铜锂和二甲基铜锂与相同的伯新戊基甲苯磺酸酯反应不同。几种仲新戊基甲苯磺酸酯与有机铜锂试剂反应，通过协同的1,2-脱氢磺化反应生成烯烃。如果无法进行抗消除，则会发生骨骼重排。
• Diastereoselective conjugate addition with acetals, oxazolidines and imidazolidines as chiral auxiliaries
  作者：A. Alexakis、R. Sedrani、P. Mangeney、J.F. Normant

  DOI：10.1016/s0040-4039(00)80509-2

  日期：1988.1

  Organocopper reagents undergo highly diastereoselective conjugate addition on cinnamates bearing a chiral oxazolidine or imidazolidine ring.

  有机铜试剂在带有手性恶唑烷或咪唑烷环的肉桂酸酯上进行高度非对映选择性的缀合物加成。
• Direct displacement and coupling of prop-2-ynylic acetates with organocuprates
  作者：Raymond S. Brinkmeyer、Timothy L. Macdonald

  DOI：10.1039/c39780000876

  日期：——

  The direct displacement of the acetate in 1-trimethylsilyl-3-acetoxyoct-1-yne (6) by the alkyl substituent of dialkylorganocuprates, and the lithium dimethylcuprate-medrated coupling of 3-acetoxy-1-trimethylsilylpent-4-en-1-yne (8b) are reported.

  乙酸被1-三甲基甲硅烷基-3-乙酰氧基辛-1-炔（6）中的乙酸直接置换为二烷基有机辛酸酯的烷基取代基，以及3-乙酰氧基-1-三甲基甲硅烷基戊-4-en-1-的二甲基cup甲基锂介导的偶联反应报道了yne（8b）。