B. Other Catalyti; Process by Transition-Metal Complexes IV. Cross-Coupling Reaction A. Coupling of 1 -Alkenylboron Derivatives: Synthesis of Conjugated Dienes 6. Coupling of Arylboron Derivatives: Synthesis of Biaryls C. Coupling of Alkylboron Derivatives D. Coupling with Triflates E. Synthesis of Vinylic Sulfides F. Coupling with lodoalkanes: Alkyl-Alkyl CouDlino G. Coupling with Other Organic Halides and Boron Reagents V. Head-to-Tail Coupling VI. Carbonylative Coupling VII. Alkoxycarbonylation and Dimerization VIII. Conclusion 2457 2458 2458

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Palladium-catalyzed cross-coupling reactions of organoboron compounds

s, or keywords if they used Heck-type chemistry in their syntheses, because it became one of basic tools of organic preparations, a natural way to

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck%20reactie%20Beletskaya%20%20Chem.%20Rev.%20003009.pdf

The heck reaction as a sharpening stone of palladium catalysis.

The increasing demand to produce enantiomerically pure pharmaceuticals, agrochemicals, flavors, and other fine chemicals has advanced the field of asymmetric catalytic technologies.1,2 Among all asymmetric catalytic methods, asymmetric hydrogenation utilizing molecular hydrogen to reduce prochiral olefins, ketones, and imines, have become one of the most efficient methods for constructing chiral compounds.3 The development of homogeneous asymmetric hydrogenation was initiated by Knowles4a and Horner4b in the late 1960s, after the discovery of Wilkinson’s homogeneous hydrogenation catalyst [RhCl(PPh3)3]. By replacing triphenylphosphine of the Wilkinson’s catalystwithresolvedchiralmonophosphines,6Knowles and Horner reported the earliest examples of enantioselective hydrogenation, albeit with poor enantioselectivity. Further exploration by Knowles with an improved monophosphine CAMP provided 88% ee in hydrogenation of dehydroamino acids.7 Later, two breakthroughs were made in asymmetric hydrogenation by Kagan and Knowles, respectively. Kagan reported the first bisphosphine ligand, DIOP, for Rhcatalyzed asymmetric hydrogenation.8 The successful application of DIOP resulted in several significant directions for ligand design in asymmetric hydrogenation. Chelating bisphosphorus ligands could lead to superior enantioselectivity compared to monodentate phosphines. Additionally, P-chiral phosphorus ligands were not necessary for achieving high enantioselectivity, and ligands with backbone chirality could also provide excellent ee’s in asymmetric hydrogenation. Furthermore, C2 symmetry was an important structural feature for developing new efficient chiral ligands. Kagan’s seminal work immediately led to the rapid development of chiral bisphosphorus ligands. Knowles made his significant discovery of a C2-symmetric chelating bisphosphine ligand, DIPAMP.9 Due to its high catalytic efficiency in Rh-catalyzed asymmetric hydrogenation of dehydroamino acids, DIPAMP was quickly employed in the industrial production of L-DOPA.10 The success of practical synthesis of L-DOPA via asymmetric hydrogenation constituted a milestone work and for this work Knowles was awarded the Nobel Prize in 2001.3k This work has enlightened chemists to realize * Corresponding author. 3029 Chem. Rev. 2003, 103, 3029−3069

New Chiral Phosphorus Ligands for Enantioselective Hydrogenation

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

Ruthenium-Catalyzed Reactions for Organic Synthesis.

Mononuclear palladium–hydroxo complexes of the type [Pd(N–N)(C6F5)(OH)]
				[(N–N = 2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (Me2bipy), or N,N,N′,N′-tetramethylethylenediamine (tmeda) react with SO2
				(1 atm) at room temperature in alcohol (methanol, ethanol, propanol or isopropanol) to yield alkyl sulfito palladium complexes [Pd(N–N)(C6F5)(SO2OR)]
				(R = Me, Et, Pr or iPr). Similar alkyl sulfito complexes [Pd(N–N)(C6F5)(SO2OR)]
				(N–N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me or Et) are obtained when [Pd(N–N)(C6F5)Cl] is treated with KOH in the corresponding alcohol ROH and SO2 is bubbled through the solution. The reaction of [Pd(bipy)(C6F5)(OH)] with SO2 in tetrahydrofuran gives [Pd(N–N)(C6F5)(SO2OH)]. The X-ray diffraction study of [Pd(tmeda)(C6F5)(SO2OPr)] has established the sulfur coordination of the propyl sulfito ligand.

Insertion reactions of SO2 into Pd–OR bonds: preparation of alkyl sulfito complexes of palladium(II)

The di-µ-carboxylato complexes [{Pd(CH2C9H6N)(µ-O2CR)}2](CH2C9H6N = 8-quinolylmethyl, R = Me or CF3) react in methanol with NaOH(aq)(1 : 1 molar ratio) to give the corresponding mixed hydroxo–carboxylato-bridged complexes [{Pd(CH2C9H6N)}2(µ-OH)(µ-O2CR)](R = Me 1 or CF32). The reactions of 1 or 2 with arylamines or thiols (1 : 1 molar ratio) yielded the corresponding amido- or thiolato-carboxylato complexes [{Pd(CH2C9H6N)}2(µ-O2CMe)(µ-NHR)](R = Ph 3, p-MeC6H44 or p-NO2C6H45) or [{Pd(CH2C9H6N)}2(µ-O2CR)(µ-SR′)](R = Me, R′= Et 6, But7, Ph 8 or p-MeC6H49; R = CF3, R′= But10). The 1H NMR data indicate a cis arrangement of the CH2C9H6N ligands. The crystal structure of complex 10 has been determined. It confirms the cis relationship of the CH2C9H6N ligands. The co-ordination at each palladium atom is approximately square planar and the oxygen atoms of the trifluoroacetate ligands are trans to carbon. The Pd2(µ-OCOCF3)(µ-SBut) core is quite bent with an angle of 55° between the two palladium co-ordination planes.

Synthesis and structural study of [{Pd(CH2C9H6N)}2(µ-O2CR)(µ-X)] complexes (R = Me or CF3; X = hydroxide, amide or thiolate)

The widely-used halothane anaesthetic CF3CHBrCl exhibits a proton magnetic resonance signal in CCl4 solution which is strongly deshielded by addition of N-methylpyrrolidone. This is interpreted as ...

Penny A. Chaloner

Papers

Insertion reactions of SO2 into Pd–OR bonds: preparation of alkyl sulfito complexes of palladium(II)

Synthesis and structural study of [{Pd(CH2C9H6N)}2(µ-O2CR)(µ-X)] complexes (R = Me or CF3; X = hydroxide, amide or thiolate)

Strong amide–halothane hydrogen-bonding observed by nuclear magnetic resonance

Crown ethers and analogues

Photoinduced electron transfer, parts A–D