A Combined Experimental/Computational Study of the Mechanism of a Palladium-Catalyzed Bora-Negishi Reaction

被引：9

作者：

Campos, Jesus ^{[1
,2
,3
,4
]}

Nova, Ainara ^{[5
]}

Kolychev, Eugene L. ^{[1
]}

Aldridge, Simon ^{[1
]}

机构：

[1] Inorgan Chem Lab, South Pk Rd, Oxford OX1 3QR, England

[2] Univ Seville, IIQ, Dept Quim Inorgan, Ave Americo Vespucio 49, Seville 41092, Spain

[3] Univ Seville, Ctr Innovac Quim Avanzada ORFEO CINQA, Ave Americo Vespucio 49, Seville 41092, Spain

[4] CSIC, Ave Americo Vespucio 49, Seville 41092, Spain

[5] Univ Oslo, CTCC, Dept Chem, POB 1033 Blindern, N-0315 Oslo, Norway

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2017年 / 23卷 / 51期

关键词：

acylboranes; borylation; borylzinc; cross-coupling; palladium; CROSS-COUPLING REACTION; DENSITY-FUNCTIONAL THEORY; NUCLEAR-MAGNETIC-RESONANCE; MOLECULAR-ORBITAL METHODS; ALKOXY DIBORON REAGENTS; ARYL HALIDES; REDUCTIVE ELIMINATION; OXIDATIVE ADDITION; HECK REACTION; BASIS-SETS;

D O I：

10.1002/chem.201702703

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Experimental and computational efforts are reported which illuminate the mechanism of a novel boron version of the widespread Negishi coupling reaction that offers a new protocol for the formation of aryl/acyl C-B bonds using a bulky boryl fragment. The role of nucleophilic borylzinc reagents in the reduction of the Pd-II pre-catalysts to Pd-0 active species has been demonstrated. The non-innocent behavior of the PPh3 ligands of the [Pd(PPh3)(2)Cl-2] pre-catalyst under activation conditions has been probed both experimentally and computationally, revealing the formation of a trimetallic Pd species bearing bridging phosphide (PPh2-) ligands. Our studies also reveal the monoligated formulation of the Pd-0 active species, which led us to synthesize related ((3)-indenyl)Pd-monophosphine catalysts which show improved catalytic performances under mild conditions. A complete mechanistic proposal to aid future catalyst developments is provided.

引用

页码：12655 / 12667

页数：13

共 175 条

[1] On the role of additives in alkyl-alkyl Negishi cross-couplings [J].

Achonduh, George T. ;

Hadei, Niloufar ;

Valente, Cory ;

Avola, Stephanie ;

O'Brien, Christopher J. ;

Organ, Michael G. .

CHEMICAL COMMUNICATIONS, 2010, 46 (23) :4109-4111

[2] Mechanism of the palladium-catalyzed homocoupling of arylboronic acids: Key involvement of a palladium peroxo complex [J].

Adamo, Carlo ;

Amatore, Christian ;

Ciofini, Ilaria ;

Jutand, Anny ;

Lakmini, Hakim .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (21) :6829-6836

[3] 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

[4] Bimetallic intermediates in the formation of nucleophilic allenylzincs from allenylpalladiums: A DFT study [J].

Alvarez, Rosana ;

de Lera, Angel R. ;

Aurrecoechea, Jose M. ;

Durana, Aritz .

ORGANOMETALLICS, 2007, 26 (11) :2799-2802

[5] Efficient oxidative carbonylation of iPrOH to oxalate catalyzed by Pd(II)-PPh3 complexes using benzoquinone as a stoichiometric oxidant [J].

Amadio, E. ;

Toniolo, L. .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2014, 767 :72-77

[6] EVIDENCE OF THE FORMATION OF ZEROVALENT PALLADIUM FROM PD(OAC)2 AND TRIPHENYLPHOSPHINE [J].

AMATORE, C ;

JUTAND, A ;

MBARKI, MA .

ORGANOMETALLICS, 1992, 11 (09) :3009-3013

[7] RATES AND MECHANISM OF THE FORMATION OF ZEROVALENT PALLADIUM COMPLEXES FROM MIXTURES OF PD(OAC)(2) AND TERTIARY PHOSPHINES AND THEIR REACTIVITY IN OXIDATIVE ADDITIONS [J].

AMATORE, C ;

CARRE, E ;

JUTAND, A ;

MBARKI, MA .

ORGANOMETALLICS, 1995, 14 (04) :1818-1826

[8] 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

[9] Mechanistic and kinetic studies of palladium catalytic systems [J].

Amatore, C ;

Jutand, A .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 576 (1-2) :254-278

[10] Rates of the oxidative addition of benzyl halides to a metallacyclic palladium(II) complex and of the reductive elimination from a benzyl-palladium(IV) complex [J].

Amatore, Christian ;

Catellani, Marta ;

Deledda, Sara ;

Jutand, Anny ;

Motti, Elena .

ORGANOMETALLICS, 2008, 27 (18) :4549-4554

← 1 2 3 4 5 6 7 8 9 10 →