N-Heterocyclic Carbenes in Late Transition Metal Catalysis

8.4.5. Nitromercuration Reactions 3878 9. Hydroamination of Alkenes and Alkynes under Microwave Irradiation 3878 * To whom correspondence should be addressed. Phone: +49 241 8

Hydroamination: direct addition of amines to alkenes and alkynes.

Dehydrogenation as a substrate-activating strategy in homogeneous transition-metal catalysis.

Concurrent tandem catalysis

140 years ago Adolf von Baeyer proposed the structure of a heteroaromatic compound which revolutionized organic and medical chemistry: indole. After more than a century, indole itself and the complexity of naturally occurring indole derivatives continue to inspire and influence developments in synthetic chemistry. In particular, the ubiquitous presence of indole rings in pharmaceuticals, agrochemicals, and functional materials are testament to the ever increasing interest in the design of mild and efficient synthetic routes to functionalized indole derivatives. This Review emphasizes the achievements in the selective catalytic functionalization of indoles (C-C bond-forming processes) over the last four years.

Catalytic Functionalization of Indoles in a New Dimension

The catalysed enantioselective formation of carbon–nitrogen bonds by the hydroamination reaction is reviewed. All examples deal with substrates containing non-activated carbon–carbon multiple bonds which are transformed either via intramolecular or intermolecular reactions. Structurally different complexes already provided nitrogen containing compounds/heterocycles with high enantioselectivities.

Asymmetric hydroamination of non-activated carbon-carbon multiple bonds.

Ytterbium and lutetium ionic complexes derived from enantiopure substituted (R)-binaphthylamine ligands, of the general formula [Li(THF)n][Ln[(R)-C20H12(NR)2]2], have been investigated for the hydroamination/cyclization of several aminopentenes and an aminohexene. Complexes with isopropyl or cyclohexyl substituents on nitrogen atoms were found to be efficient catalysts under mild conditions for the formation of N-containing heterocycles with enantiomeric excesses up to 78%.

Enantioselective intramolecular hydroamination catalyzed by lanthanide ate complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands.

New preparations of lanthanide alkoxides and their catalytical activity in Meerwein-Ponndorf-Verley-Oppenauer reactions

A new family of lanthanide ionic complexes derived from chiral, substituted (R)-binaphthylamine ligands, [Li(thf)4][Ln{(R)-C20H12(NR)2}2] (Ln=Yb, Sm, Nd, or Lu), has been synthesized and characterized by X-ray crystal structure analyses. All complexes have been tested as new catalysts for the hydroamination/cyclization of 1-(aminomethyl)-1-allylcyclohexane. Ytterbium complexes proved to be both the most active and the most enantioselective, and the use of the complex [Li(thf)4][Yb{(R)-C20H12(NC3H7)2}2], bearing isopropyl radicals on the nitrogen atoms, allowed the formation of the corresponding spiropyrrolidine in high yield with up to 70 % ee.

Lanthanide complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands in the catalysis of enantioselective intramolecular hydroamination.

Jacqueline Collin

Papers

Asymmetric hydroamination of non-activated carbon-carbon multiple bonds.

Enantioselective intramolecular hydroamination catalyzed by lanthanide ate complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands.

New preparations of lanthanide alkoxides and their catalytical activity in Meerwein-Ponndorf-Verley-Oppenauer reactions

Lanthanide complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands in the catalysis of enantioselective intramolecular hydroamination.

Enantioselective ring opening of meso-epoxides by aromatic amines catalyzed by lanthanide iodo binaphtholates.