Hydrovinylation and Related Reactions: New Protocols and Control Elements in Search of Greater Synthetic Efficiency and Selectivity

RajanBabu, T. V.; Nomura, Nobuyoshi; Jin, Jian; Radetich, Branko; Park, Haengsoon; Nandi, Mahasweta

doi:10.1002/(sici)1521-3765(19990702)5:7<1963::aid-chem1963>3.0.co;2-4

Cited by 64 publications

(44 citation statements)

References 10 publications

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“…The field of asymmetric nickel-catalyzed hydrovinylation of styrene derivatives has been dominated by phosphoruscontaining ligands, [57,367,440] and remarkable progress was made with the introduction of monodentate azaphospholene ligands in the late 1990s. [368,369] However, it was not until 2002 that phosphoramidite ligands were introduced for this transformation.…”

Section: Hydrovinylationsmentioning

confidence: 99%

Phosphoramidites: Privileged Ligands in Asymmetric Catalysis

Teichert¹,

Feringa²

2010

Angew Chem Int Ed

648

350

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Asymmetric catalysis with transition-metal complexes is the basis for a vast array of stereoselective transformations and has changed the face of modern synthetic chemistry. Key to this success has been the design of chiral ligands to control the regio-, diastereo-, and enantioselectivity. Phosphoramidites have emerged as a highly versatile and readily accessible class of chiral ligands. Their modular structure enables the formation of ligand libraries and easy fine-tuning for a specific catalytic reaction. Phosphoramidites frequently show exceptional levels of stereocontrol, and their monodentate nature is essential in combinatorial catalysis, where a ligand-mixture approach is used. In this Review, recent developments in asymmetric catalysis with phosphoramidites used as ligands are discussed, with a focus on the formation of carbon-carbon and carbon-heteroatom bonds.

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Section: Hydrovinylationsmentioning

confidence: 99%

Phosphoramidites: Privileged Ligands in Asymmetric Catalysis

Teichert¹,

Feringa²

2010

Angew Chem Int Ed

648

350

View full text Add to dashboard Cite

show abstract

“…In this context, the hydrovinylation reaction can be defined as an heterodimerisation between ethylene gas and an activated olefin, usually styrene (and other vinylarenes) or norbornene [1], catalysed by a transition metal complex [2,3]. Scheme 1 shows the hydrovinylation of the model substrate, styrene, and some of the byproducts often encountered.…”

Section: Introductionmentioning

confidence: 99%

P-Stereogenic monophosphines in Pd-catalysed enantioselective hydrovinylation of styrene

Grabulosa

Mannu

Muller

et al. 2011

Journal of Organometallic Chemistry

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“…The differences between the 13 C chemical shifts of these two atoms are small (<2 ppm), as found in similar complexes. [7] In the 1 H NMR spectra, the four resonances of the allylic H atoms appeared as two broad singlets, corresponding to the syn protons and two doublets, corresponding to the anti protons ( 2 J H,P [9][10][11][12]. The preparation of Pd4′ in pure form was not possible because it was always contaminated with around 25 % of neutral Pd4.…”

Section: Preparation Of Cationic Pd Complexes Pd1′-13′mentioning

confidence: 99%

Neutral and Cationic Palladium Complexes of P‐Stereogenic Phosphanes Bearing a Heterocyclic Substituent

et al. 2016

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The coordination chemistry of 13 optically pure P‐stereogenic diarylmonophosphanes P(Het)PhR [Het = 4‐dibenzofuranyl (DBF), 4‐dibenzothiophenyl (DBT), 4‐dibenzothiophenyl S,S‐dioxide (DBTO2) and 1‐thianthrenyl (TA); R = OMe, Me, iPr, Fc (ferrocenyl)] to Pd‐allyl moieties is described. Both neutral [PdCl(η3‐(2‐methylallyl)(κP‐P)] and cationic [Pd{η3‐(2‐methylallyl)(κP‐P)2}]PF6 complexes have been prepared. Coordination of the heteroatom of the heterocycle was only possible in the case of TA‐based phosphanes; these furnished complexes of the type [Pd{η3‐(2‐methylallyl)(κ2P,S‐P)}]PF6 after chloride abstraction with TlPF6. The crystal structure of the complex [Pd(η3‐2‐methylallyl)(κ2P,S‐PPh(OMe)(1‐TA)]PF6 is reported. The neutral Pd complexes were found to be highly active in the hydrovinylation of styrene after activation with AgBF4, except for the TA‐based phosphanes. The cationic Pd complexes were evaluated in allylic alkylation and amination with the model substrate rac‐trans‐1,3‐diphenylprop‐2‐enyl acetate (rac‐I), achieving total conversions and up to 70 % ee.

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Hydrovinylation and Related Reactions: New Protocols and Control Elements in Search of Greater Synthetic Efficiency and Selectivity

Cited by 64 publications

References 10 publications

Phosphoramidites: Privileged Ligands in Asymmetric Catalysis

Phosphoramidites: Privileged Ligands in Asymmetric Catalysis

P-Stereogenic monophosphines in Pd-catalysed enantioselective hydrovinylation of styrene

Neutral and Cationic Palladium Complexes of P‐Stereogenic Phosphanes Bearing a Heterocyclic Substituent

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