Homogeneous Nickel-Catalyzed Olefin Hydrocyanation

Tolman, Chadwick A.; McKinney, Ronald J.; Seidel, W. C.; Druliner, J. D.; Stevens, W.R.

doi:10.1016/s0360-0564(08)60257-6

Cited by 159 publications

(87 citation statements)

References 59 publications

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“…The most prominent example is the twofold addition of HCN to butadiene, known as the DuPont adiponitrile process. [2] During the past decade, the asymmetric hydrocyanation of norbornene and vinylarenes has also attracted new interest as a potentially versatile route to chiral nitriles, amines, and acids. [3] The most successful ligand systems employed in these reactions are based on binaphthyl-, [4] sugar-, [5] xanthene-, [6] or triptycene-derived [7] backbones.…”

Section: Introductionmentioning

confidence: 99%

Lewis Acid Controlled Regioselectivity in Styrene Hydrocyanation

Bini

Pidko

Müller

et al. 2009

Chemistry A European J

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According to present knowledge, the Ni-catalyzed hydrocyanation of styrene leads predominantly to the branched product 2-phenylpropionitrile (98 %). We observed a dramatic inversion of the regioselectivity upon addition of a Lewis acid. Up to 83 % of the linear product 3-phenylpropionitrile was obtained by applying phosphite ligands in the presence of AlCl(3). The mechanism of the Ni-catalyzed reaction and the influence of additional Lewis acids have been investigated by means of deuterium labeling experiments, NMR studies, and DFT calculations. Furthermore, the behavior of different Lewis acids, such as CuCN, could be rationalized and predicted by DFT calculations.

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Section: Introductionmentioning

confidence: 99%

Lewis Acid Controlled Regioselectivity in Styrene Hydrocyanation

Bini

Pidko

Müller

et al. 2009

Chemistry A European J

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“…Thermodynamics favours 3PN (about 9:1) and 2M3BN may be isomerized to 3PN in the presence of a nickel catalyst, through a CACN bond breaking/forming reaction involving a Ni(II) allyl cyanide complex. The selective anti-Markovnikov addition of the second HCN to yield AdN requires the concurrent isomerization of 3PN to 4-pentenenitrile (4PN) and HCN addition to 4PN, in presence of a Ni(0) complex and Lewis acids (LA) as co-catalysts [3,4].…”

Section: Introductionmentioning

confidence: 99%

Isomerization of 2-methyl-3-butenenitrile with (bis-diphenylphosphinoferrocene)nickel compounds: Catalytic and structural studies

Acosta-Ramírez

Muñoz‐Hernández

Jones

et al. 2006

Journal of Organometallic Chemistry

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“…Present address: Ciba-Geigy AG, Pharma Division, CH4002 Basel. Examples are the hydroformylation and the hydrocyanation of C=C bonds using Rh [l] and Ni [2] catalysts, respectively. For review on hydrosilylations, see [13].…”

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confidence: 99%

Catalytic Enantioselective Hydrosilylation of Aromatic Ketones Using Rhodium Complexes of TADDOL‐Derived Cyclic Phosphonites and Phosphites

Sakaki

Schweizer²,

Seebàch³

1993

Helvetica Chimica Acta

104

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Cyclic phosphonites and phosphites 2 4 are readily available from CI2PR and (R,R)-or (S,S)-a,a,a ',a '-tetraaryl-l,3-dioxolane-4,5-dimethanols ( = TADDOLs 1, which, in turn, are only two steps away from tartrate); the X-ray crystal structure of one representative, the phenyl phosphonite Zb, was determined. Five previously described and six new ones of the chiral P derivatives were tested as ligands for RhI-and Pdo-catalyzed reactions such as hydrocarbonylations, hydroborations, and hydrosilylations of C=C bonds; while the resulting catalysts were highly active and regioselective, they did not lead to useful enantiomer enrichment in the products (Scheme 1 ) . In contrast, hydrosilylation of phenyl and 2-naphthyl methyl or ethyl ketone by Ph,SiH, (1.2 equiv.) gave, after desilylation, the corresponding secondary alcohols of (R)-configuration with up to 87 % ee in the presence of 0.1 equiv. of the penta(2-naphthyl)-substituted phosphonite 3d and 0.02 mol-equiv. of Rh (Table 1 ).

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Homogeneous Nickel-Catalyzed Olefin Hydrocyanation

Cited by 159 publications

References 59 publications

Lewis Acid Controlled Regioselectivity in Styrene Hydrocyanation

Lewis Acid Controlled Regioselectivity in Styrene Hydrocyanation

Isomerization of 2-methyl-3-butenenitrile with (bis-diphenylphosphinoferrocene)nickel compounds: Catalytic and structural studies

Catalytic Enantioselective Hydrosilylation of Aromatic Ketones Using Rhodium Complexes of TADDOL‐Derived Cyclic Phosphonites and Phosphites

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