The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes

被引：58
作者：
Ahlquist, Marten
Fabrizi, Giancarlo
Cacchi, Sandro
Norrby, Per-Ola
机构：
[1] Tech Univ Denmark, Dept Chem, DK-2800 Lyngby, Denmark
[2] Univ Roma La Sapienza, Dipartimento Chim & Tecnol Sostanze Biologicament, I-00185 Rome, Italy
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2006年 / 128卷 / 39期
关键词：
D O I：
10.1021/ja061543x
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The mechanism of the Pd-catalyzed hydroarylation and hydrovinylation reaction of alkynes has been studied by a combination of experimental and theoretical methods (B3LYP), with an emphasis on the phosphine-free version. The regioselectivity of the hydroarylation and hydrovinylation shows unexpected differences, which could be attributed mainly to the higher steric demand of the cyclohexenyl group as compared to the phenyl group. Hydroarylation of alpha,beta-acetylenic carbonyl substrates yields a very unusual anti-Michael selectivity, which is shown to result from reaction of the nonconjugated double bond, leaving the conjugation intact. In all cases were the regioselectivities reproduced by the calculations.
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页码：12785 / 12793
页数：9
相关论文
共 48 条
[1]   An experimental and theoretical study of the mechanism of stannylcupration of α,β-acetylenic ketones and esters [J].
Ahlquist, M ;
Nielsen, TE ;
Le Quement, S ;
Tanner, D ;
Norrby, PO .
CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (10) :2866-2873
[2]   On the performance of continuum solvation models for the solvation energy of small anions [J].
Ahlquist, M ;
Kozuch, S ;
Shaik, S ;
Tanner, D ;
Norrby, PO .
ORGANOMETALLICS, 2006, 25 (01) :45-47
[3]   Palladium(0) alkyne complexes as active species: a DFT investigation [J].
Ahlquist, M ;
Fabrizi, G ;
Cacchi, S ;
Norrby, PO .
CHEMICAL COMMUNICATIONS, 2005, (33) :4196-4198
[4]   Theoretical evidence for low-ligated palladium(0): [Pd-L] as the active species in oxidative addition reactions [J].
Ahlquist, M ;
Fristrup, P ;
Tanner, D ;
Norrby, PO .
ORGANOMETALLICS, 2006, 25 (08) :2066-2073
[5]   ROLE AND EFFECTS OF HALIDE-IONS ON THE RATES AND MECHANISMS OF OXIDATIVE ADDITION OF IODOBENZENE TO LOW-LIGATED ZEROVALENT PALLADIUM COMPLEXES PD0(PPH3)2 [J].
AMATORE, C ;
AZZABI, M ;
JUTAND, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (22) :8375-8384
[6]   MECHANISM OF OXIDATIVE ADDITION OF PALLADIUM(0) WITH AROMATIC IODIDES IN TOLUENE, MONITORED AT ULTRAMICROELECTRODES [J].
AMATORE, C ;
PFLUGER, F .
ORGANOMETALLICS, 1990, 9 (08) :2276-2282
[7]   Anionic Pd(0) and Pd(II) intermediates in palladium-catalyzed Heck and cross-coupling reactions [J].
Amatore, C ;
Jutand, A .
ACCOUNTS OF CHEMICAL RESEARCH, 2000, 33 (05) :314-321
[8]   Theoretical insight into the C-C coupling reactions of the vinyl, phenyl, ethynyl, and methyl complexes of palladium and platinum [J].
Ananikov, VP ;
Musaev, DG ;
Morokuma, K .
ORGANOMETALLICS, 2005, 24 (04) :715-723
[9]  
Arcadi A, 1999, EUR J ORG CHEM, V1999, P3305, DOI 10.1002/(SICI)1099-0690(199912)1999:12<3305::AID-EJOC3305>3.0.CO
[10]  
2-O
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