Catalytic carbene insertion into C-H bonds.

1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis

Catalytic enantioselective C-H activation by means of metal-carbenoid-induced C-H insertion.

Recent Advances in Asymmetric Catalytic Metal Carbene Transformations.

C-H oxidation has a long history and an ongoing presence in research at the forefront of chemistry and interrelated fields. As such, numerous highly useful articles and reviews have been written on this subject. Logically, these are generally written from the perspective of the scope and limitations of the reagents employed. This Minireview instead attempts to emphasize chemoselectivity imposed by the nature of the substrate. Consequently, many landmark discoveries in the field of C-H oxidation are not discussed, but hopefully the perspective taken herein will allow C-H oxidation reactions to be more readily incorporated into synthetic planning.

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If C-H bonds could talk: selective C-H bond oxidation.

Carboxylate and carboxamide ligands of dirhodium(II) catalysts control chemoselectivity in competitive metal carbene transformations of diazo compounds. For competitive intramolecular cyclopropanation versus intramolecular aromatic substitution with 1-diazo-3-aryl-5-hexen-2-ones, use of Rh 2 (OAc) 4 results in the products from both transformations in nearly equal amounts, but dirhodium(II) perfluorobutyrate (Rh 2 (pfb) 4 ) provides only the aromatic substitution product while dirhodium(II) caprolactamate (Rh 2 (cap) 4 ) gives only the cyclopropanation product

Ligand effects on dirhodium(II) carbene reactivities. Highly effective switching between competitive carbenoid transformations

Monomeric organolithium compounds in tetrahydrofuran: tert-butyllithium, sec-butyllithium, supermesityllithium, mesityllithium, and phenyllithium. Carbon-lithium coupling constants and the nature of carbon-lithium bonding

Structure-selectivity comparisons are made between chiral dirhodium(II) tetrakis(methyl 2-oxopyrrolidine-5-carboxylaten), Rh 2 (5S-MEPY) 4 and Rh 2 (5R-MEPY) 4 (5), and dirhodium(II) tetrakis(4-benzyl-2-oxazolidinones), Rh 2 (4R-BNOX) 4 and Rh 2 (45-BNOX) 4 (6), to ascertain and understand their relative effectiveness as catalysts for enantiocontrol in metal-carbene transformations. The syntheses, spectral characteristics, and X-ray structures for these dirhodium(II) compounds are reported. Each possesses two oxygen- and two nitrogen-donor atoms bound to each octahedral rhodium with a cis orientation of the nitrogen ligands

Dirhodium(II) tetrakis(carboxamidates) with chiral ligands. Structure and selectivity in catalytic metal-carbene transformations

Enantiocontrol and regiocontrol in lactam syntheses by intramolecular carbon-hydrogen insertion reactions of diazoacetamides catalyzed by chiral rhodium(II) carboxamides

William R. Winchester

Papers

Ligand effects on dirhodium(II) carbene reactivities. Highly effective switching between competitive carbenoid transformations

Monomeric organolithium compounds in tetrahydrofuran: tert-butyllithium, sec-butyllithium, supermesityllithium, mesityllithium, and phenyllithium. Carbon-lithium coupling constants and the nature of carbon-lithium bonding

Dirhodium(II) tetrakis(carboxamidates) with chiral ligands. Structure and selectivity in catalytic metal-carbene transformations

Enantiocontrol and regiocontrol in lactam syntheses by intramolecular carbon-hydrogen insertion reactions of diazoacetamides catalyzed by chiral rhodium(II) carboxamides

Dynamics of solvated lithium(+) within exo,exo-[1,3-bis(trimethylsilyl)allyl]lithium N,N,N',N'-tetramethylethylenediamine complex