AbstractDirect alkylation of a methyl group, on di- and trisubstituted ureas, with terminal alkenes by C(sp3)−H bond activation proceeded in the presence of a hydroxoiridium/bisphosphine catalyst to give high yields of the corresponding addition products. The hydroxoiridium/bisphosphine complex generates an amidoiridium intermediate by reaction with ureas having an N−H bond.

AbstractDirect alkylation of a methyl group, on di- and trisubstituted ureas, with terminal alkenes by C(sp3)−H bond activation proceeded in the presence of a hydroxoiridium/bisphosphine catalyst to give high yields of the corresponding addition products. The hydroxoiridium/bisphosphine complex generates an amidoiridium intermediate by reaction with ureas having an N−H bond.

AbstractIridium-catalyzed hydroarylation of alkenyl ethers, such as allylic and homoallylic ethers, by C−H bond activation gave high yields of the corresponding addition products, where the aryl groups were selectively installed at the α-carbon atom to the alkoxy group. The reaction involves an isomerization of the alkenyl ethers into the corresponding 1-alkenyl ethers, which then undergo the regio- and enantioselective hydroarylation.

AbstractIridium-catalyzed hydroarylation of alkenyl ethers, such as allylic and homoallylic ethers, by C−H bond activation gave high yields of the corresponding addition products, where the aryl groups were selectively installed at the α-carbon atom to the alkoxy group. The reaction involves an isomerization of the alkenyl ethers into the corresponding 1-alkenyl ethers, which then undergo the regio- and enantioselective hydroarylation.

Catalytic asymmetric hydroarylation of vinyl ethers using 2-aryl-substituted azoles containing an N–H bond as directing groups was realized by use of a hydroxoiridium/chiral phosphine catalyst. The reaction proceeded via C–H activation of the aromatic ring to give high yields of the corresponding addition products with high branch- and enantioselectivity.

Asymmetric alkylation of N-sulfonylbenzamides with vinyl ethers via a directed C–H bond activation gave high yields of the corresponding addition products with high branch- and enantioselectivity.

Iridium/chiral diene complexes efficiently catalyzed the asymmetric cyclization of N-sulfonyl alkenyl amides to give the corresponding 2-pyrrolidone derivatives with high enantioselectivity. A mechanistic study revealed that the reaction proceeds via nucleophilic attack of the amide on the alkene moiety.

A cationic iridium/binap catalyst enabled the asymmetric [3+2] annulation of cyclic N-acyl ketimines with internal alkynes via C–H activation to give spiroaminoindene derivatives with high enantioselectivity. The stereochemical course of this annulation was switchable by acid additives.

Selective H/D exchange at vinyl and methylidene groups of alkenes with D2O was promoted by an iridium catalyst generated in situ from a hydroxoiridium complex and N-mesylbenzamide.

Iridium-catalyzed hydroarylation of vinyl ethers via a directed C–H bond activation of aromatic compounds gave high yields of the corresponding addition products with high branch selectivity.

A hydroxoiridium complex coordinated with 1,5-cyclooctadiene efficiently catalyzed the hydroacylation of bicyclic alkenes with 2-hydroxybenzaldehyde and its derivatives in high yields with high stereoselectivity.

Asymmetric cyclization of alkenoic acids was realized by the use of an iridium/chiral bisphosphine catalyst, giving high yields of the corresponding γ-lactones with good enantioselectivity.

Rhodium-catalyzed asymmetric addition of cyclopropylboronic acids to electron-deficient alkenes such as alkenylsulfones, enones, enoates, and nitroalkenes proceeded to give high yields of the corresponding 1,4-addition products with high enantioselectivity.

The catalytic addition of terminal alkynes to 3,3-diarylcyclopropenes in the presence of a Rh(I)/binap complex proceeded to give the cycloaddition products in good yields, where a 1,4-Rh shift is involved as a key step.

Rhodium/chiral diene complex-catalyzed asymmetric addition of arylboronic acids to cyclic ketimines having an ester group proceeded to give the corresponding α-amino acid derivatives in high yields with high enantioselectivity. The cyclic amino acid derivative was transformed into a linear α,α-diaryl-substituted α-N-methylamino acid ester.

Iridium-catalyzed annulation of salicylimines with 1,3-dienes gave high yields of the corresponding 4-aminochromanes with high stereoselectivity. The use of a chiral diene ligand enabled the asymmetric reaction to give 4-aminochromanes with high enantioselectivity.

[3 + 2] Annulation of ketimines with internal and terminal alkynes proceeded via C–H activation to give aminoindene derivatives in high yields, which is catalyzed by a cationic iridium complex coordinated with 1,5-cyclooctadiene (cod).

Ir-catalyzed [3 + 2] annulation of cyclic N-sulfonyl ketimines with 1,3-dienes, in which an aryliridium intermediate is formed via C–H activation, gives aminoindane derivatives in high yields with high regio- and diastereoselectivity.

Enantioselective [3 + 2] annulation between 1,3-dienes and N-acyl ketimines in situ generated from 3-aryl-3-hydroxyisoindolin-1-ones proceeded via C–H activation to give spiroaminoindane derivatives in high yields with high regio- and enantioselectivity, which is realized by use of an Ir/chiral diene catalyst.

Asymmetric addition of arylboronates to aryl-substituted cyclic ketimines proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of sulfamidates and sulfamides with high enantioselectivity (up to 99% ee).

The asymmetric addition of silylacetylenes to 1,1-disubstituted allenes proceeded in the presence of a cobalt/chiral bisphosphine ligand to give the corresponding enynes with high enantioselectivity. The results of deuterium-labeling experiments indicated that a hydrogen atom at the chiral center is originated from the terminal alkyne, and they were in good agreement with the proposed catalytic cycle where enantioselectivity is determined by the reaction of the proposed π-allylcobalt intermediate with the terminal alkyne.

Asymmetric addition of arylboronic acids to α,β-unsaturated sulfonyl compounds proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of the addition products with high enantioselectivity (96–>99.5% ee). The diene ligand was proved to be essential for the formation of the addition products, while the use of a bisphosphine ligand mainly gave the cine-substitution product.

Asymmetric addition of (triisopropylsilyl)acetylene to α,β,γ,δ-unsaturated carbonyl compounds took place in the presence of a cobalt/Duphos catalyst to give the 1,6-addition products in high yields with high regio- and enantioselectivity.

Asymmetric addition of silylacetylenes to meso-oxa- and azabenzonorbornadienes took place in the presence of a cobalt/QuinoxP* catalyst to give the addition products in good yields with high enantioselectivity.

Asymmetric addition of arylboroxines to δ-aryl-α,β,γ,δ-unsaturated ketones proceeded in the presence of an iridium catalyst coordinated with a chiral diene ligand to give high yields of δ-diaryl ketones with very high enantioselectivity.

A hydroxorhodium complex coordinated with a chiral diene ligand catalyzed the asymmetric addition of trimethylboroxine to N-sulfonylarylimines to give high yields of chiral 1-aryl-1-ethylamines with high enantioselectivity.N-(1-(4-Chlorophenyl)ethyl)-4-methylbenzenesulfonamideC15H16ClNO2SEe = 99%[α]D20=-79 (c 0.55, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)N-(1-(3-Chlorophenyl)ethyl)-4-methylbenzenesulfonamideC15H16ClNO2SEe = 98%[α]D20=-73 (c 0.50, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)N-(1-(2-Chlorophenyl)ethyl)-4-methylbenzenesulfonamideC15H16ClNO2SEe = 99%[α]D20=-53 (c 0.40, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)N-(1-(4-Bromophenyl)ethyl)-4-methylbenzenesulfonamideC15H16BrNO2SEe = 98%[α]D20=-62 (c 0.33, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)4-Methyl-N-(1-(4-(trifluoromethyl)phenyl)ethyl)benzene-sulfonamideC16H16F3NO2SEe = 99%[α]D20=-49 (c 0.51, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)N-(1-(4-Methoxyphenyl)ethyl)-4-methylbenzenesulfonamideC16H19NO3SEe = 99%[α]D20=-82 (c 0.51, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)N-(1-(2-Methoxyphenyl)ethyl)-4-methylbenzenesulfonamideC16H19NO3SEe = 98%[α]D20=-66 (c 0.42, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)4-Methyl-N-(1-(naphthalen-1-yl)ethyl)benzenesulfonamideC19H19NO2SEe = 97%[α]D20=+14 (c 0.52, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)4-Methyl-N-(1-(naphthalen-2-yl)ethyl)benzenesulfonamideC19H19NO2SEe = 98%[α]D20=-79 (c 0.46, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)N-(1-(4-Chlorophenyl)ethyl)-4-nitrobenzenesulfonamideC14H13ClN2O4SEe = 98%[α]D20=-37 (c 0.56, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)N-(1-(4-Methoxyphenyl)ethyl)-4-nitrobenzenesulfonamideC15H16N2O5SEe = 98%[α]D20=-32 (c 0.47, CHCl3).Source of chirality: asymmetric methylationAbsolute configuration: (S)

Catalytic addition of silylacetylenes to α,β-unsaturated ketones proceeded in the presence of a cobalt complex coordinated with a bisphosphine ligand to give high yields of β-alkynylketones.

Asymmetric addition of arylboroxines to β-alkoxyacrylate esters proceeded in the presence of a rhodium complex coordinated with a chiral diene ligand to give high yields of β-alkoxy-β-arylcarboxylic acid esters with very high enantioselectivity.

Oxidative alkynylation of acrylate esters with propargylic alcohols giving conjugated enyne esters was realized by use of a diene–rhodium catalyst. Propargylic alcohols were found to be useful alkynylating reagents in the present reaction to produce alkynylrhodium species via carbon–carbon bond cleavage. An excess of the acrylate ester worked as a hydride acceptor to reproduce the active rhodium species.

Cyclopolymerization of nitrogen-bridged 1,8-diynes containing one terminal and one internal alkyne in the presence of a rhodium/chiral diene catalyst gave enantiomerically enriched polymers with a helix chirality that keep their chiral structures in solution. This polymerization proceeded through alternating reaction of the terminal and the internal alkynes, forming polyacetylenes with a 1,2-dialkylidene heterocyclic unit.

Rhodium-catalyzed asymmetric 1,6-addition of arylboronic acids to β-alkynyl acrylamides substituted with a silyl group on the alkyne terminus took place to give high yields of axially chiral allenylsilanes with 94−99% enantioselectivity, which was realized by use of a rhodium/chiral diene complex.

Iridium-catalyzed asymmetric 1,6-addition of arylboroxines to α,β,γ,δ-unsaturated carbonyl compounds to give δ-arylated carbonyl compounds in high yields with 90−99% enantioselectivity was realized by use of an iridium/chiral diene complex.

Asymmetric addition of (triisopropylsilyl)acetylene to nitroalkenes took place in the presence of a rhodium/chiral bisphosphine catalyst to give β-alkynylated nitroalkanes in high yields with high enantioselectivity.

The reaction of alkynoates with aryl- or alkylboron reagents in the presence of a rhodium/diene catalyst gave high yields of salicylate derivatives with high selectivity, which consist of three or four molecules of the alkynoate and one organic group derived from the organoboron reagents.

Asymmetric addition of terminal alkynes to allenyl aldehydes took place in the presence of an acetylacetonate complex [Rh(acac)L∗] (L∗ = binap or segphos) as a catalyst to give indanol derivatives in high yields with high regio- and enantioselectivity. The acetylacetonate (acac) ligand on the rhodium is important for the selective formation of the indanol derivatives.2-(4-(Triphenylsilyl)but-1-en-3-yn-2-yl)indan-1-olC31H26OSiEe = 99%[α]D20=-45 (c 0.99, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)6-Methoxy-2-(4-(triphenylsilyl)but-1-en-3-yn-2-yl)indan-1-olC32H28O2SiEe = 97%[α]D20=-14 (c 0.98, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)5-Methoxy-2-(4-(triphenylsilyl)but-1-en-3-yn-2-yl)indan-1-olC32H28O2SiEe = 99%[α]D20=-39 (c 0.77, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)6-Fluoro-2-(4-(triphenylsilyl)but-1-en-3-yn-2-yl)indan-1-olC31H25FOSiEe = 99%[α]D20=-35 (c 0.74, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)2-Methyl-2-(4-(triphenylsilyl)but-1-en-3-yn-2-yl)indan-1-olC32H28OSiEe = 81%[α]D20=-32 (c 0.70, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)2-(4-(Triisopropylsilyl)but-1-en-3-yn-2-yl)indan-1-olC22H32OSiEe = 98%[α]D20=-55 (c 0.80, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)2-(5-(Methoxymethoxy)-5,5-diphenylpent-1-en-3-yn-2-yl)indan-1-olC28H26O3Ee = 95%[α]D20=-20 (c 0.94, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S, 2R)2-(4-Phenylbut-1-en-3-yn-2-yl)indan-1-olC19H16OEe = 98%[α]D20=-33 (c 0.93, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)2-(4-(4-Methoxyphenyl)but-1-en-3-yn-2-yl)indan-1-olC20H18O2Ee = 99%[α]D20=-58 (c 0.65, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)2-(4-(Naphthalen-1-yl)but-1-en-3-yn-2-yl)indan-1-olC23H18OEe = 98%[α]D20=-65 (c 0.80, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)2-(1-(1-(4-Chlorophenyl)-1,2,3-triazol-4-yl)vinyl)indan-1-yl acetateC21H18ClN3O2Ee = 99%[α]D20=-232 (c 0.35, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R)

Rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to β-phthaliminoacrylate esters took place efficiently to give high yields of β-aryl-β-amino acid esters with 96−99% enantioselectivity, which was realized by use of a hydroxorhodium/chiral diene complex.

Asymmetric conjugate alkynylation of α,β-unsaturated ketones with (triisopropylsilyl)ethynylsilanols giving β-alkynylketones took place in high yields with high enantioselectivity in the presence of chiral rhodium catalysts.

New C2-symmetric tetrafluorobenzobarrelene ligands were prepared and applied successfully to the rhodium-catalyzed asymmetric addition of arylboronic acids to aromaticaldehydes giving chiral diarylmethanols in high yield with high enantioselectivity.

The rhodium-catalyzed intermolecular asymmetric hydroalkoxylation and hydrosulfenylation of diphenylphosphinylallenes gave chiral allylicphosphine oxides substituted with vinylether and thioether moieties in high yields with high enantioselectivities.

Asymmetric addition of arylboroxines to cyclic N-sulfonyl ketimines proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of benzosultams, where a triaryl-substituted stereogenic carbon center was created with high enantioselectivity (93–99% ee). The chiral benzosultams were transformed into the chiral (triaryl)methylamines by breaking the cyclic structure.

Asymmetric addition of arylboroxines to δ-aryl-α,β,γ,δ-unsaturated ketones proceeded in the presence of an iridium catalyst coordinated with a chiral diene ligand to give high yields of δ-diaryl ketones with very high enantioselectivity.

Catalytic asymmetric hydroarylation of vinyl ethers using 2-aryl-substituted azoles containing an N–H bond as directing groups was realized by use of a hydroxoiridium/chiral phosphine catalyst. The reaction proceeded via C–H activation of the aromatic ring to give high yields of the corresponding addition products with high branch- and enantioselectivity.

Rhodium-catalyzed asymmetric addition of cyclopropylboronic acids to electron-deficient alkenes such as alkenylsulfones, enones, enoates, and nitroalkenes proceeded to give high yields of the corresponding 1,4-addition products with high enantioselectivity.

A cationic iridium/binap catalyst enabled the asymmetric [3+2] annulation of cyclic N-acyl ketimines with internal alkynes via C–H activation to give spiroaminoindene derivatives with high enantioselectivity. The stereochemical course of this annulation was switchable by acid additives.

A hydroxoiridium complex coordinated with 1,5-cyclooctadiene efficiently catalyzed the hydroacylation of bicyclic alkenes with 2-hydroxybenzaldehyde and its derivatives in high yields with high stereoselectivity.

Asymmetric cyclization of alkenoic acids was realized by the use of an iridium/chiral bisphosphine catalyst, giving high yields of the corresponding γ-lactones with good enantioselectivity.

[3 + 2] Annulation of ketimines with internal and terminal alkynes proceeded via C–H activation to give aminoindene derivatives in high yields, which is catalyzed by a cationic iridium complex coordinated with 1,5-cyclooctadiene (cod).

Asymmetric addition of arylboronates to aryl-substituted cyclic ketimines proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of sulfamidates and sulfamides with high enantioselectivity (up to 99% ee).

The reaction of alkynoates with aryl- or alkylboron reagents in the presence of a rhodium/diene catalyst gave high yields of salicylate derivatives with high selectivity, which consist of three or four molecules of the alkynoate and one organic group derived from the organoboron reagents.

Asymmetric addition of silylacetylenes to meso-oxa- and azabenzonorbornadienes took place in the presence of a cobalt/QuinoxP* catalyst to give the addition products in good yields with high enantioselectivity.

Catalytic addition of silylacetylenes to α,β-unsaturated ketones proceeded in the presence of a cobalt complex coordinated with a bisphosphine ligand to give high yields of β-alkynylketones.

Asymmetric addition of arylboroxines to β-alkoxyacrylate esters proceeded in the presence of a rhodium complex coordinated with a chiral diene ligand to give high yields of β-alkoxy-β-arylcarboxylic acid esters with very high enantioselectivity.

Asymmetric addition of (triisopropylsilyl)acetylene to nitroalkenes took place in the presence of a rhodium/chiral bisphosphine catalyst to give β-alkynylated nitroalkanes in high yields with high enantioselectivity.

The rhodium-catalyzed intermolecular asymmetric hydroalkoxylation and hydrosulfenylation of diphenylphosphinylallenes gave chiral allylicphosphine oxides substituted with vinylether and thioether moieties in high yields with high enantioselectivities.

New C2-symmetric tetrafluorobenzobarrelene ligands were prepared and applied successfully to the rhodium-catalyzed asymmetric addition of arylboronic acids to aromaticaldehydes giving chiral diarylmethanols in high yield with high enantioselectivity.

Enantioselective [3 + 2] annulation between 1,3-dienes and N-acyl ketimines in situ generated from 3-aryl-3-hydroxyisoindolin-1-ones proceeded via C–H activation to give spiroaminoindane derivatives in high yields with high regio- and enantioselectivity, which is realized by use of an Ir/chiral diene catalyst.

Rhodium/chiral diene complex-catalyzed asymmetric addition of arylboronic acids to cyclic ketimines having an ester group proceeded to give the corresponding α-amino acid derivatives in high yields with high enantioselectivity. The cyclic amino acid derivative was transformed into a linear α,α-diaryl-substituted α-N-methylamino acid ester.