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Volumn 352, Issue 17, 2010, Pages 2979-2992

Acid-free nickel catalyst for stereo- and regioselective hydrophosphorylation of alkynes: Synthetic procedure and combined experimental and theoretical mechanistic study

Author keywords

alkynes; homogeneous catalysis; nickel complexes; phosphorylation; selectivity

Indexed keywords


EID: 78649588433     PISSN: 16154150     EISSN: 16154169     Source Type: Journal    
DOI: 10.1002/adsc.201000606     Document Type: Article
Times cited : (76)

References (153)
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    • In the literature selectivity was often defined as a simple ratio between Markovnikov and anti-Markovnikov products (Scheme1), while the other by-products are neglected. Although such calculations gave higher selectivity values, catalyst optimization resulted in lower isolated yields due to formation of other by-products. Throughout the present study the material balance on phosphorus species was verified in each experiment (the product, unreacted H-phosphonate and overall amount of by-products)
    • In the literature selectivity was often defined as a simple ratio between Markovnikov and anti-Markovnikov products (Scheme1), while the other by-products are neglected. Although such calculations gave higher selectivity values, catalyst optimization resulted in lower isolated yields due to formation of other by-products. Throughout the present study the material balance on phosphorus species was verified in each experiment (the product, unreacted H-phosphonate and overall amount of by-products).
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    • Nickel complexes are known to catalyze alkyne polymerization
    • Nickel complexes are known to catalyze alkyne polymerization
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    • Formation of a broad signal is an indication of complexation to the metal center (or exchange), see
    • Formation of a broad signal is an indication of complexation to the metal center (or exchange), see
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    • In the present study we did not investigate the influence of the metal salt on by-products formation, since in the optimized conditions high product yields were obtained
    • In the present study we did not investigate the influence of the metal salt on by-products formation, since in the optimized conditions high product yields were obtained.
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    • External nucleophilic attack is more common for π-complexes of divalent metal derivatives, although involvement of π-complexes of zero-valent metal derivatives can not be excluded. In the studied system Ni(II) and Ni(0) centers can be readily interconverted by oxidative addition/reductive elimination of the P-H bond (in Scheme3 ligands on Ni are omitted for clarity)
    • External nucleophilic attack is more common for π-complexes of divalent metal derivatives, although involvement of π-complexes of zero-valent metal derivatives can not be excluded. In the studied system Ni(II) and Ni(0) centers can be readily interconverted by oxidative addition/reductive elimination of the P-H bond (in Scheme3 ligands on Ni are omitted for clarity).
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    • [12,16-18]), for the calculations here the simple model with X=H was utilized
    • [12,16-18]), for the calculations here the simple model with X=H was utilized.
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    • At the moment it is not possible to unambiguously rule out either of the pathways due to known limitations of calculation accuracy. See the reviews for a discussion of the accuracy of density functional calculations for studying reaction mechanisms of transition metal-catalyzed transformations
    • At the moment it is not possible to unambiguously rule out either of the pathways due to known limitations of calculation accuracy. See the reviews for a discussion of the accuracy of density functional calculations for studying reaction mechanisms of transition metal-catalyzed transformations
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    • n species are generated by ligand exchange reaction (see Scheme3 and related discussion)
    • n species are generated by ligand exchange reaction (see Scheme3 and related discussion).
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.