The effect of catalyst loading in copper-catalyzed cyclohexane functionalization by carbene insertion

被引:17
作者
Caballero, Ana
Diaz-Requejo, M. Mar
Trofimenko, Swiatoslaw
Belderrain, Tomas R.
Perez, Pedro J.
机构
[1] Univ Huelva, Dept Quim & Ciencia Mat, CSIC, Unidad Asociada Lab Catalisis Homogenea, E-21007 Huelva, Spain
[2] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA
关键词
copper; C-H activation; homogeneous catalysis; carbenes; N ligands;
D O I
10.1002/ejic.200600811
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A study of the variables that affect the insertion of the :CHCO2Et group (formed from ethyl diazocetate, EDA) into the C-H bonds of cyclohexane in the presence of a Tp(x)Cu complex as the catalyst (Tp(x) = trispyrazolylborate ligand) has demonstrated an anomalous effect of the catalyst loading. The use of low concentrations of catalyst produces an increase in the yield of the C-H activation product ethyl cyclohexaneacetate. This effect has also been found in the case of other less elaborated catalysts such as [Bp(Br3)Cu] or [(bipy)(2)Cu][I]. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007.
引用
收藏
页码:2848 / 2852
页数:5
相关论文
共 26 条
[1]   CHEMISTRY OF THE GROUP 1B ELEMENTS .8. COMPLEXES OF COPPER(I) OR SILVER(I) CONTAINING ONLY POLY(PYRAZOLYL)BORATE LIGANDS [J].
BRUCE, MI ;
WALSH, JD .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1979, 32 (12) :2753-2756
[2]   Functionalization of carbon-hydrogen bonds of hydrocarbons and ethers via carbene insertion with copper(I)-homoscorpionate catalysts [J].
Caballero, A ;
Díaz-Requejo, MM ;
Belderraín, TR ;
Nicasio, MC ;
Trofimenko, S ;
Pérez, PJ .
ORGANOMETALLICS, 2003, 22 (20) :4145-4150
[3]   Highly regioselective functionalization of aliphatic carbon-hydrogen bonds with a perbromohomoscorpionate copper(I) catalyst [J].
Caballero, A ;
Díaz-Requejo, MM ;
Belderraín, TR ;
Nicasio, MC ;
Trofimenko, S ;
Pérez, PJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (06) :1446-1447
[4]   Discrete bridging and terminal copper carbenes in copper-catalyzed cyclopropanation [J].
Dai, XL ;
Warren, TH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (32) :10085-10094
[5]   Catalytic enantioselective C-H activation by means of metal-carbenoid-induced C-H insertion [J].
Davies, HML ;
Beckwith, REJ .
CHEMICAL REVIEWS, 2003, 103 (08) :2861-2903
[6]   Direct synthesis of a bis(pyrazolyl)boratocopper(I) complex:: Synthesis and characterization of [H2B(3,5-(CF3)2Pz)2]Cu(PPh3)2 displaying an unusual coordination mode for a poly(pyrazolyl)borate ligand [J].
Dias, HVR ;
Lu, HL .
INORGANIC CHEMISTRY, 2000, 39 (10) :2246-+
[7]   Silver(I) scorpionate mediated insertion of carbenes into aliphatic C-H bonds [J].
Dias, HVR ;
Browning, RG ;
Richey, SA ;
Lovely, CJ .
ORGANOMETALLICS, 2004, 23 (06) :1200-1202
[8]   Kinetics of the BpCu-catalyzed carbene transfer reaction (Bp equals dihydridobis(1-pyrazolyl)borate).: Is a 14-electron species the real catalyst for the general copper-mediated olefin cyclopropanation? [J].
Díaz-Requejo, MM ;
Belderrain, TR ;
Nicasio, MC ;
Prieto, F ;
Pérez, PJ .
ORGANOMETALLICS, 1999, 18 (14) :2601-2609
[9]   Intermolecular copper-catalyzed carbon-hydrogen bond activation via carbene insertion [J].
Díaz-Requejo, MM ;
Belderraín, TR ;
Nicasio, MC ;
Trofimenko, S ;
Pérez, PJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (06) :896-897
[10]   Copper(I)-homoscorpionate catalysts for the preferential, kinetically controlled cis cyclopropanation of α-olefins with ethyl diazoacetate [J].
Díaz-Requejo, MM ;
Caballero, A ;
Belderraín, TR ;
Nicasio, MC ;
Trofimenko, S ;
Pérez, PJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (06) :978-983