Yoichiro Kuninobu

A rhenium complex, [ReBr(CO)(3)(thf)](2), catalyzes the reaction of an aromatic aldimine with an isocyanate and an acetylene to give a phthalimidine and an indene derivative in a quantitative yield, respectively. The reactions proceed via C-H bond activation, insertion of the isocyanate or the acetylene, intramolecular nucleophilic cyclization to the aldimine of the generated amido- or alkenyl-rhenium species, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are u

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTOrganic Reactions Catalyzed by Rhenium Carbonyl ComplexesYoichiro Kuninobu* and Kazuhiko Takai*View Author Information Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Kita-ku, Okayama 700-8530, Japan*E-mail:[email protected]; [email protected]Cite this: Chem. Rev. 2011, 111, 3, 1938–1953Publication Date (Web):November 23, 2010Publication History Received28 July 2010Published online

A rhenium complex, [ReBr(CO)3(thf)]2, catalyzes the reaction of an aromatic aldimine with an acetylene to give an indene derivative in a quantitative yield. The reaction proceeds via C-H bond activation, insertion of the acetylene, intramolecular nucleophilic cyclization, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the intramolecular nucleophilic cyclization of the alkenylmetal speci

Si goes chiral: Treatment of a bis(biphenyl)silane with a catalytic amount of a rhodium complex gave a spirosilabifluorene bearing a quaternary silicon atom. By using a rhodium catalyst with a chiral phosphine ligand (see scheme), asymmetric dehydrogenative cyclization proceeded to give chiral derivatives in good yields and enantioselectivities.

Mn gets in the game: In the presence of a manganese catalyst and a stoichiometric amount of hydrosilane, aldehydes insert into CH bonds of aromatic rings of compounds with directing groups (see scheme). This first example of a manganese-catalyzed chemical transformation through CH bond activation gives silyl ethers in good to excellent yields and can also be applied to asymmetric transformation.

The first copper-catalyzed intramolecular C(sp(3))-H and C(sp(2))-H oxidative amidation has been developed. Using a Cu(OAc)2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp(3))-H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various β-lactams were obtained in excellent yield, even on gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere in dimethyl sulfoxide, howev

A rhenium complex, [ReBr(CO)3(thf)]2, catalyzed reactions of aromatic ketimines with aldehydes to give isobenzofuran derivatives in good to excellent yields. In contrast to ruthenium and rhodium catalysts, aldehydes, which are polar unsaturated molecules, inserted into the C-H bond after activation by the rhenium complex.

An iridium/bipyridine-catalyzed ortho-selective C-H borylation of aryl sulfides was developed. High ortho-selectivity was achieved by a Lewis acid-base interaction between a boryl group of the ligand and a sulfur atom of the substrate. This is the first example of a catalytic and regioselective C-H transformation controlled by a Lewis acid-base interaction between a ligand and a substrate. The C-H borylation reaction could be conducted on a gram scale, and with a bioactive molecule as a substrat

Dibenzophosphole oxides were obtained from secondary hydrophosphine oxides with a biphenyl group by dehydrogenation via phosphine-hydrogen and carbon-hydrogen bond cleavage in the presence of a catalytic amount of palladium(II) acetate, Pd(OAc)(2). By using this reaction, a ladder-type dibenzophosphole oxide could also be synthesized by double intramolecular dehydrogenative cyclization.

Several reaction steps, including CH activation, lead to indene derivatives in good yields in the rhenium-catalyzed reaction of aromatic ketimines and ethyl acrylate. Indene derivatives can also be obtained by the reactions of aromatic ketones with α,β-unsaturated esters in the presence of a catalytic rhenium complex and p-anisidine (see scheme). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z503627_s.pdf or from the author.

Aminoindane derivatives were synthesized diastereoselectively by the treatment of aromatic imines with allenes in the presence of a catalytic amount of a rhenium complex, [HRe(CO)(4)](n). The allenes inserted into the aromatic C-H bonds.

A rhenium complex, [ReBr(CO)3(thf)]2, catalyzes the reaction of a 1,3-dicarbonyl cyclic compound with an acetylene to give a medium-sized cyclic compound in excellent yield. By using isocyanide as an additive, the catalytic activity of the rhenium complex changes dramatically, and the insertion of acetylenes into a carbon-carbon single bond occurs under mild conditions. A plausible mechanism is that the reaction proceeds via the formation of a rhenacyclopentene intermediate, ring opening by a re

[reaction: see text] A rhenium complex, [ReBr(CO)(3)(thf)](2), catalyzed the intermolecular reactions of 1,3-dicarbonyl compounds with terminal acetylenes and gave the corresponding alkenyl derivatives in excellent yields. These reactions could apply to an intramolecular version and gave the corresponding cyclic compounds quantitatively.

Polycyclic aromatic compounds can be synthesized from 2-benzylic- or 2-allylbenzaldehydes using a catalytic amount of In(III) or Re(I) complexes. By using this method, polycyclic aza-aromatic compounds can also be prepared efficiently. In these reactions, only water is formed as a side product.