First Cyclic Carbodiphosphoranes of Copper(I) and Gold(I) and Their Application in the Catalytic Cleavage of X−H Bonds (X = N and O)

Corberán, Rosa; Marrot, Sébastien; Dellus, Nicolas; Merceron-Saffon, Nathalie; Kato, Tsuyoshi; Peris, Eduardo; Baceiredo, Antoine

doi:10.1021/om8008958

Cited by 61 publications

(34 citation statements)

References 66 publications

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“…Both complexes were explored for the anti-Markovnikov hydroamination of acrylonitrile with aniline (Scheme 15.59). The Cu(I) system provided higher conversions to product over the Au(I) complex, and under the reaction conditions explored, only the Cu catalyst yielded high conversions under an argon atmosphere [257].…”

Section: Intermolecular Alkene Hydroaminationmentioning

confidence: 95%

Transition‐Metal‐Catalyzed Hydroamination Reactions

Schafer

Yim

Yonson

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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Section: Intermolecular Alkene Hydroaminationmentioning

confidence: 95%

Transition‐Metal‐Catalyzed Hydroamination Reactions

Schafer

Yim

Yonson

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…4,5 Previous approaches towards anti-Markovnikov hydroamination have traditionally involved activated olefins or intramolecular transformations. 6,7,8,9,10,11 However, in 1999 the Beller group disclosed the first example of transition metal-catalyzed anti-Markovnikov hydroamination of olefins; this seminal study accomplished a low-yielding hydroamination of styrenes with secondary aliphatic amines using rhodium catalysis. 12 More recently, some success in the metal-catalyzed intermolecular anti-Markovnikov hydroamination of unactivated olefins has been reported.…”

Section: Introductionmentioning

confidence: 99%

Formal anti-Markovnikov hydroamination of terminal olefins

Bronner

Grubbs

2014

Chem. Sci.

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A new strategy to access linear amines from terminal olefin precursors is reported. This two-step, one-pot hydroamination methodology employs sequential oxidation and reduction catalytic cycles. The formal hydroamination transformation proceeds with excellent regioselectivity, and only the anti-Markovnikov product is observed. Up to 70% yield can be obtained from styrenes or aliphatic olefins and either primary or secondary aromatic amines. Additionally, the scope is broad with respect to the olefin and accommodates a variety of functionalities; we demonstrate that amines with removable aryl protecting groups may be utilized to allow access to a more diverse array of hydroamination adducts.

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“…10 Thorough bonding analyses on the isovalent triphosphenium ions and carbodiphosphoranes confirm the presence of "lone pairs" of electrons in frontier orbitals; 11,12 however, the latter have far more precedent to act as a ligand to transition metals and also to main group Lewis acids. [13][14][15][16][17][18][19][20] Of particular note is the ability of B to donate four electrons simultaneously to electron-deficient fragments such as {Ni(CO) 2 } (C), {BH 2 } + (D), {GeCl} + , and {PNR 2 } 2+ (E) that cannot be isolated with one traditional two-electron donor ligand (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Utilizing a zwitterionic approach for the synthesis of late transition metal – triphosphenium ion coordination compounds

et al. 2015

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Zwitterionic dicoordinate phosphorus(I) compounds (1 and 2), formally a charge neutral triphosphenium ion or phosphanide, are shown to coordinate to a variety of late transition metals. The reaction of the phosphanide proligands with {Rh(COD)Cl} 2 results in an equilibrium process that varies as a function of temperature or reaction stoichiometry. Palladium(II) compounds have a tendency to chlorinate the borate backbone while giving dimeric coordination compounds (1Pd) and also a decomposition product (3) where the P(I) atom was replaced. Both "lone pairs" of electrons on phosphorus are utilized simultaneously in the dominant product from the reaction of 1 and [PtMe 2 (-SMe 2 )] 2 , while each platinum center ortho-metallated a phenyl substituent on the flanking phosphorus atoms (1Pt). Stable, isolable, and fully characterized dimeric mercury complexes (1Hg and 2Hg) are produced nearly quantitatively from the reaction of the phosphanide proligand with HgCl 2 . All compounds described were structurally characterized using single crystal X-ray diffraction and represent a growing series of zwitterionic P(I) coordination compounds that cannot be isolated when a cationic triphosphenium ion is used. Résumé :Les composés zwitterioniques bis-coordonnés de phosphore(I) (1 et 2), qui sont en fait des ions triphosphénium neutres ou des phosphanures, se sont révélés capables de se coordonner à divers métaux de transition de fin de série. La réaction des proligands phosphanures avec le complexe [Rh(COD)Cl] 2 entraîne un processus d'équilibre qui varie en fonction de la tempéra-ture ou de la stoechiométrie de la réaction. Les composés de palladium(II) ont tendance à chlorer la chaîne principale boratée et à donner, pour leur part, les composés de coordination dimériques (1Pd) ainsi que le produit de décomposition (3) dans lequel l'atome de P(I) a été remplacé. Les deux doublets non liants des électrons du phosphore sont engagés simultanément dans le produit majoritaire provenant de la réaction entre le composé 1 et le complexe [PtMe 2 (-SMe 2 )] 2 . Quant aux noyaux de platine, chacun d'eux s'est inséré en position ortho de l'un des substituants phényles de l'atome de phosphore voisin (1Pt). Des complexes dimériques de mercure (1Hg et 2Hg) stables, isolables et entièrement caractérisés sont produits de façon quasi quantitative par la réaction du proligand phosphanure avec le HgCl 2 . Tous les composés décrits ont été structurellement caractérisés par diffraction des rayons X d'un cristal unique et représentent une série en expansion de composés zwitterioniques de coordination P(I) ne pouvant pas être isolés lorsqu'un cation triphosphénium est utilisé. [Traduit par la Rédaction] Mots-clés : phosphore, zwitterions, chimie de coordination, chimie des éléments du groupe principal.

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First Cyclic Carbodiphosphoranes of Copper(I) and Gold(I) and Their Application in the Catalytic Cleavage of X−H Bonds (X = N and O)

Cited by 61 publications

References 66 publications

Transition‐Metal‐Catalyzed Hydroamination Reactions

Transition‐Metal‐Catalyzed Hydroamination Reactions

Formal anti-Markovnikov hydroamination of terminal olefins

Utilizing a zwitterionic approach for the synthesis of late transition metal – triphosphenium ion coordination compounds

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