α-Phosphino Amino Acids: Synthesis, Structure, and Reactivity of Phosphaprolines

Heinicke, Joachim; Basvani, Kaleswara R.; Jones, Peter G.

doi:10.1080/10426507.2010.515956

Cited by 8 publications

(3 citation statements)

References 18 publications

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“…The particularity of heterocyclic α-phosphanyl amino acid− based ligand 46, combining the acido-basic property of amino acids with the ability of the phosphine donors to chelate a transition metal complex, prompted Heinicke et al 132 to investigate their reactivity in the oligomerization of ethylene. However, in the presence of Ni(COD) 2 , the activity of the catalytic system decreases compared with linear α-phosphanyl amino acids.…”

Section: Monoanionic Ligandsmentioning

confidence: 99%

Nickel Catalyzed Olefin Oligomerization and Dimerization

et al. 2020

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Brought to life more than half a century ago and successfully applied for high-value petrochemical intermediates production, nickel-catalyzed olefin oligomerization is still a very dynamic topic, with many fundamental questions to address and industrial challenges to overcome. The unique and versatile reactivity of nickel enables the oligomerization of ethylene, propylene and butenes into a wide range of oligomers that are highly sought-after in numerous fields to be controlled. Interestingly, both homogeneous and heterogeneous nickel catalysts have been scrutinized and employed to do this. This rare specificity encouraged us to interlink them in this review so as to open up opportunities for further catalyst development and innovation. An in-depth understanding of the reaction mechanisms in play is essential to being able to fine-tune the selectivity and achieve efficiency in the rational design of novel catalytic systems. This review thus provides a complete overview of the subject, compiling the main fundamental/industrial milestones and remaining challenges facing homogeneous/heterogeneous approaches as well as emerging catalytic concepts, with a focus on the last 10 years.

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Section: Monoanionic Ligandsmentioning

confidence: 99%

Nickel Catalyzed Olefin Oligomerization and Dimerization

et al. 2020

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“…It should be noted here that the 2,3-dihydro-1,3-benzazaphospholes are kinetically less stable than the aromatic benzazaphospholes. Slow chromatography on silica gel led to major decomposition of the dihydrobenzaphosphole-2-carboxylic acid, while storage in solution or flash chromatography may cause acid-catalyzed isomerization, as observed also for 1,3-azaphospholidine-2-carboxylic acids . This proceeds probably via slow ring-opening/ring-closure reactions at the aminophosphinoacetalic structure unit.…”

Section: Resultsmentioning

confidence: 80%

“…In comparison to nickel catalysts based on N-substituted diphenylphosphinoglycine or 3-phenyl-1,3-azaphospholidine-2-carboxylic acid, the efficiency of 12a , b /Ni for ethylene conversion is improved. Therefore, and because incorporation of styrene comonomers into the CH 2 chain was observed for o -phosphinophenolate nickel catalysts, we tested if copolymerization of ethylene with styrene is possible.…”

Section: Resultsmentioning

confidence: 99%

Enantiomerically Pure N Chirally Substituted 1,3-Benzazaphospholes: Synthesis, Reactivity toward tBuLi, and Conversion to Functionalized Benzazaphospholes and Catalytically Useful Dihydrobenzazaphospholes

et al. 2014

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Catalytic C−P coupling of chiral o-bromoanilines 1a−c to the corresponding o-phosphonoanilines 2a−c, reduction to the phosphines 3a−c, and final acid-catalyzed cyclocondensation represents a convenient access to the title compounds 4a−c. Reaction of 4a,b with tBuLi allows solventdependent directed lithiation leading either to 2-lithiobenzazaphospholes with a −PCLi−NR− substructure (in Et 2 O/ KOtBu), in the case of anisyl substitution accompanied by partial additional lithiation in o-position of the MeO-group, or to regiospecific "normal" addition with formation of −P-(tBu)−CHLi−NR− species. These were trapped by ClSiMe 3 , CO 2 , or MeOH to give the corresponding substitution products 7b, 8b, 10b, 11a,b and 12a,b, respectively. 12a,b, containing the P−C−COOH structural unit, forms with Ni(COD) 2 in THF very efficient ethylene oligomerization catalysts with high selectivity for linear α-olefins. The structure elucidation of the products is based on conclusive solution NMR data and crystal structure analyses of the 1-(1S)-anisylethyl compounds 3b and 4b.

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Electron‐Rich Aromatic 1,3‐Heterophospholes – Recent Syntheses and Impact of High Electron Density at σ²P on the Reactivity

Heinicke

2015

Eur J Inorg Chem

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This account reviews recent syntheses, properties, and the reactivity of electron‐rich aromatic 1,3‐heterophospholes, with the focus on benzazaphospholes, but also with inclusion of 1,2,4‐diazaphospholes containing the N–C=P–C motif and related O‐ and S‐containing heterocycles. Effects of the high electron density at phosphorus, a consequence of the position of the lone‐pair donating nitrogen atom in conjugation with dicoordinated (σ2) phosphorus and of the absence of P–N bonds, are illuminated by comparison of selected properties and reactions with those of less electron‐rich heterophospholes and phosphinines. Particular features of the electron‐rich heterocycles are CH‐lithiations of the P=CH fragment by tBuLi without addition at the P=C double bond in polar media, occurrence of inverse addition besides normal addition in less polar solutions, P‐alkylation and catalytic P‐arylation, and – last but not least – the avoidance of σ‐coordination of non‐zerovalent d10 transition metals within the ring plane in favor of μ2‐P and/or tilted η1‐P coordination.

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α-Phosphino Amino Acids: Synthesis, Structure, and Reactivity of Phosphaprolines

Cited by 8 publications

References 18 publications

Nickel Catalyzed Olefin Oligomerization and Dimerization

Nickel Catalyzed Olefin Oligomerization and Dimerization

Enantiomerically Pure N Chirally Substituted 1,3-Benzazaphospholes: Synthesis, Reactivity toward tBuLi, and Conversion to Functionalized Benzazaphospholes and Catalytically Useful Dihydrobenzazaphospholes

Electron‐Rich Aromatic 1,3‐Heterophospholes – Recent Syntheses and Impact of High Electron Density at σ²P on the Reactivity

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α-Phosphino Amino Acids: Synthesis, Structure, and Reactivity of Phosphaprolines

Cited by 8 publications

References 18 publications

Nickel Catalyzed Olefin Oligomerization and Dimerization

Nickel Catalyzed Olefin Oligomerization and Dimerization

Enantiomerically Pure N Chirally Substituted 1,3-Benzazaphospholes: Synthesis, Reactivity toward tBuLi, and Conversion to Functionalized Benzazaphospholes and Catalytically Useful Dihydrobenzazaphospholes

Electron‐Rich Aromatic 1,3‐Heterophospholes – Recent Syntheses and Impact of High Electron Density at σ2P on the Reactivity

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Electron‐Rich Aromatic 1,3‐Heterophospholes – Recent Syntheses and Impact of High Electron Density at σ²P on the Reactivity