Cu(I)-amido complexes in the Ullmann reaction: reactions of Cu(I)-amido complexes with iodoarenes with and without autocatalysis by CuI.
Cu(I)-amido complexes in the Ullmann reaction: reactions of Cu(I)-amido complexes with iodoarenes with and without autocatalysis by CuI.
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DOI：
10.1021/ja105695s
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发表时间：
2010-11-17
影响因子：
15
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Giri R;Hartwig JF
合成了一系列无辅助配体和含邻菲咯啉（phen）配体的Cu（I）-氨基配合物。这些配合物与碘代芳烃反应形成芳胺产物，这些数据与催化Ullmann胺化反应中的这种配合物的中间性一致。Cu（I）-氨基络合物与碘代芳烃的化学计量反应是自催化的，在反应期间产生的游离CuI充当催化剂。碘代芳烃与Cu（I）-酰胺化物、-亚胺化物和-酚盐的反应没有观察到这种自催化行为。这些配合物在各种条件下对两种空间上不同的芳基卤的选择性意味着自催化反应通过形成缺乏phen的高反应性[CuNPh 2]n来进行。与自由基探针的反应表明，苯基连接的Cu（I）-酰胺配合物与碘代芳烃的反应发生没有芳基的中间体。碘代芳烃与Cu（I）物质的氧化加成的DFT计算与碘代芳烃与在DMSO中缺乏phen的CuNPh 2物质的反应比与phen连接的LCuNPh 2的反应更快一致。计算的PhI与（DMSO）CuNPh 2反应的自由能垒为21.8 kcal/mol，而计算的PhI与（phen）CuNPh 2反应的自由能垒为33.4 kcal/mol。
A series of Cu(I)-amido complexes both lacking ancillary ligands and containing 1,10-phenanthroline (phen) as ligand have been prepared. These complexes react with iodoarenes to form arylamine products, and these data are consistent with the intermediacy of such complexes in catalytic Ullmann amination reactions. The stoichiometric reactions of the Cu(I)-amido complexes with iodoarenes are autocatalytic, with the free CuI generated during the reaction serving as the catalyst. Such autocatalytic behavior was not observed for reactions of iodoarenes with Cu(I)-amidates, -imidates and -phenoxides. The selectivity of these complexes for two sterically distinct aryl halides under various conditions imply that the autocatalytic reaction proceeds by forming highly-reactive [CuNPh2]n lacking phen. Reactions with radical probes imply that the reactions of phen-ligated Cu(I)-amido complexes with iodoarenes occur without the intermediacy of aryl radicals. DFT calculations of the oxidative addition of iodoarenes to Cu(I) species are consistent with faster reactions of iodoarenes with CuNPh2 species lacking phen in DMSO than with phen-ligated LCuNPh2. The free energy barrier computed for reaction of PhI with (DMSO)CuNPh2 was 21.8 kcal/mol, while the free energy barrier computed for reaction of PhI with (phen)CuNPh2 was 33.4 kcal/mol.
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影响因子：
5.2
作者：
Kwong, FY;Buchwald, SL
通讯作者：
Buchwald, SL
DOI：
10.1039/dt9870001883
发表时间：
1987-08-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
影响因子：
--
作者：
GAMBAROTTA, S;BRACCI, M;GUASTINI, C
通讯作者：
GUASTINI, C
影响因子：
15
作者：
Blue, ED;Davis, A;White, PS
通讯作者：
White, PS
DOI：
10.1139/v85-019
发表时间：
1985-01-01
期刊：
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE
影响因子：
--
作者：
COUTURE, C;PAINE, AJ
通讯作者：
PAINE, AJ
影响因子：
4.6
作者：
HOPE, H;POWER, PP
通讯作者：
POWER, PP