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.

Unexpected substitution reactions of bis(phosphine)platinum ethene complexes

The course of micelle-catalysed reactions at millimolar concentrations in aqueous solution may be followed by Fourier transform n.m.r. Micelles of the histidine-bearing surfactant (4a) react rapidly with p-nitrophenyl acetate in phosphate-buffered media between pD 7 and 8, entirely by acyl transfer to the imidazole with no concurrent general-base catalysis. The resulting acylimidazole breaks down by a pH-independent route between pD 7.0 and 7.9 forming both acetate ion and monoacetyl phosphate, the latter by reaction with the counter-ion of the buffer. In similar reactions of p-nitrophenyl N-acetylphenylalanine with (4a) no acylimidazole intermediate is observed. The surfactant hydroxamic acid (5a) is also readily acylated by p-nitrophenyl acetate in the same pH region, and the resulting acylhydroxamate is unstable to hydrolysis. This latter reaction is pH-dependent and exhibits a solvent isotope effect of 2.7 at pH(pD) 7.9. Addition of (5a) to the acylimidazole intermediate derived from (4a) causes rapid acyl transfer, although the latter does not affect the rate of acylhydroxamate hydrolysis.

Acyl transfer reactions in functional micelles studied by proton magnetic resonance at 270 MHz

Synthesis and structural determination of the stable dinuclear carbonyl-phosphite rhodium(0) complex: (CO)2(P(O-o-tBuPh)3)Rh-Rh(P(O-o-tBuPh)3)(CO)3

The preceeding chapter described many homogeneous reductions involving molecular hydrogen (hydrogenation reactions). However, there is an alternative type of reduction reaction where the hydrogen is supplied by a donor molecule, DH2, which itself undergoes dehydrogenation during the course of the reaction (equation 3.1).

Homogeneous Transfer Hydrogenation Catalysed by Metal Complexes

Homogeneous hydrogenation reactions have been used widely in organic synthesis, both of the industrial and laboratory scale. [1–5]. Early workers used the reactions in the most obvious sense, to remove unwanted carbon-carbon double bonds, but recent years have seen much more interesting developments, particularly in the areas of diastereoselective and enantioselective reductions, and in stereoselective reduction of carbonyl groups. In research applications the platinum group metals have provided most of the catalysts, but in considering larger scale applications of the reactions it will be necessary in future to be aware of cost, particularly in view of the very large fluctuations in the price of rhodium over recent years.

Penny A. Chaloner

Papers

Unexpected substitution reactions of bis(phosphine)platinum ethene complexes

Acyl transfer reactions in functional micelles studied by proton magnetic resonance at 270 MHz

Synthesis and structural determination of the stable dinuclear carbonyl-phosphite rhodium(0) complex: (CO)2(P(O-o-tBuPh)3)Rh-Rh(P(O-o-tBuPh)3)(CO)3

Homogeneous Transfer Hydrogenation Catalysed by Metal Complexes

Homogeneous Hydrogenation in Organic Synthesis