Iridium-Catalyzed 1,3-Dipolar Cycloadditions

Carmona, Daniel; Oro, Luis A.

doi:10.1007/978-3-642-15334-1_8

Cited by 5 publications

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“…One of the most attractive methodologies to obtain optically active organic compounds involves cycloaddition reactions, in which several adjacent stereogenic centers can be created in a concerted fashion . Among them, the enantioselective 1,3-dipolar cycloaddition (DC) reaction of an alkene and a nitrone affords five-membered isoxazolidines containing up to three contiguous asymmetric carbon atoms (Scheme a) and the Diels–Alder (DA) reaction between an alkene and a diene can generate up to four contiguous stereogenic centers within a cyclohexene framework (Scheme b) …”

Section: Introductionmentioning

confidence: 99%

Chiral Octahedral Phosphano–Oxazoline Iridium(III) Complexes as Catalysts in Asymmetric Cycloaddition Reactions

et al. 2013

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The synthesis and characterization of cationic iridium(III) aqua complexes of the formula [IrH(H 2 O)(PN*)(PP)][SbF 6 ] 2 (PN* = chiral phosphano−oxazoline ligand; PP = diphosphane) as well as that of the OPOF 2 -containing complex [IrH(OPOF 2 )(PNiPr)(dppp)][SbF 6 ] (10) are reported. The X-ray molecular structures of [IrH(H 2 O)-(PNInd)(dppe)][SbF 6 ] 2 (1), [IrH(H 2 O)(PNInd)(dppen)][SbF 6 ] 2 (2), and 10a have been determined. Dichloromethane solutions of these aqua complexes efficiently catalyze the enantioselective 1,3-dipolar cycloaddition of the nitrone N-benzylidenephenylamine N-oxide to methacrolein and Diels−Alder reactions between cyclopentadiene and trans-β-nitrostyrenes. In the first case, the catalytic reaction occurs with excellent endo selectivity and ee up to 85%; the Diels−Alder reaction occurs rapidly at room temperature with good endo:exo selectivity and ee up to 90%. The dipolar cycloaddition intermediates [IrH(methacrolein)(PNInd)(PP)][SbF 6 ] 2 (PP = (S,S)-chiraphos ( 11), (R)-prophos ( 12)) have been characterized, and the molecular structure of 11 has been determined by an X-ray structural analysis.

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Section: Introductionmentioning

confidence: 99%

Chiral Octahedral Phosphano–Oxazoline Iridium(III) Complexes as Catalysts in Asymmetric Cycloaddition Reactions

et al. 2013

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ChemInform Abstract: Iridium‐Catalyzed 1,3‐Dipolar Cycloadditions

Carmona

Oro

2011

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Asymmetric 1,3-dipolar cycloaddition reactions between methacrylonitrile and nitrones catalysed by well-defined M(diphosphane) (M=Rh, Ir) complexes

Carmona

Viguri

Asenjo

et al. 2016

Tetrahedron: Asymmetry

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The cationic half-sandwich aqua-complexes [(η 5-C 5 Me 5)M(PP*)(H 2 O)][SbF 6 ] 2 [M= Rh, Ir; PP*= (R)-Benphos, (R)-Cyphos, (2R,4R)-Norphos] catalyse the 1,3-dipolar cycloaddition reaction (DCR) of nitrones with methacrylonitrile with perfect regioselectivity, low-to-perfect endo selectivity and low-to-moderate enantioselectivity. The active species involved in the catalytic process, [(η 5-C 5 Me 5)M(PP*)(methacrylonitrile)][SbF 6 ] 2 , have been isolated and characterised as mixtures of the (S)-and (R)-at-metal epimers. NMR measurements of these mixtures indicated that the (R M)-isomers epimerise to the corresponding (S M) counterparts. The molecular structure of the rhodium complex (S Rh ,R C)-[(η 5-C 5 Me 5)Rh{(R)-Benphos}(methacrylonitrile)][SbF 6 ] 2 has been determined by X-ray diffraction methods. Diastereopure (S Rh ,R C)-[(η 5-C 5 Me 5)Rh(PP*)(methacrylonitrile)][SbF 6 ] 2 compounds catalyse stoichiometrically the above mentioned DCR with up to 90% enantiomeric excess, showing the influence of the metal handeness on the catalytic stereochemical outcome. Catalysts can be recycled up to three times without significant loss of either activity or selectivity.

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Iridium-Catalyzed 1,3-Dipolar Cycloadditions

Cited by 5 publications

References 45 publications

Chiral Octahedral Phosphano–Oxazoline Iridium(III) Complexes as Catalysts in Asymmetric Cycloaddition Reactions

Chiral Octahedral Phosphano–Oxazoline Iridium(III) Complexes as Catalysts in Asymmetric Cycloaddition Reactions

ChemInform Abstract: Iridium‐Catalyzed 1,3‐Dipolar Cycloadditions

Asymmetric 1,3-dipolar cycloaddition reactions between methacrylonitrile and nitrones catalysed by well-defined M(diphosphane) (M=Rh, Ir) complexes

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