Regioselective Metal‐Catalyzed Hydrophosphinylation of Alkynes: Synthesis of Enantiopure α‐ or β‐Substituted Vinylphosphane Oxides

Duraud, Amélie; Toffano, Martial; Fiaud, Jean‐Claude

doi:10.1002/ejoc.200900658

Cited by 30 publications

(12 citation statements)

References 37 publications

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“…The products of the addition along Markownikoff rule were shown to be available in the presence of palladium and nickel catalyst as was reported by Tanaka [8][9][10][11][12], Han [13,14], Montchamp [15][16][17], Toffano [18] and in our publications [19][20][21].…”

supporting

confidence: 65%

“…The alkyne insertion into the metal-hydrogen bond was formerly presumed only for the rhodium complexes, and this reaction resulted in the other product, antiMarkownikoff isomer in the case of terminal alkynes [18,25,26]. And the explanation of the Markownikoff regioselectivity in the reactions catalyzed by palladium and nickel complexes was based just on the suggestion of the insertion into the metal-phosphorus bond.…”

Section: The Comparison Of Addition Of Molecules Possessing P(v)-h Bondmentioning

confidence: 96%

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The comparison of addition of molecules possessing P(V)-H bond to alkynes catalyzed with Pd and Ni complexes

2010

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Main factors have been analyzed necessary for creation of an effi cient catalytic system for alkynes hydrophosphorylation based on nickel complexes, and a valid model system was suggested for the comparison with palladium complexes. It has been discovered for the fi rst time that the insertion of an alkyne into the metalhydrogen bond occurs with a considerably lower activation barrier than into the metal-phosphorus bond, whereas the variation in the reaction energy corresponds in both cases to an exothermic reaction. Under the optimized conditions the transformation catalyzed by nickel complexes does not require acid addition and may proceed even in the absence of a phosphine ligand.The hydroheterofunctionalization (the addition of molecules containing a bond hydrogen-heteroatom) of unsaturated organic compounds is among the leading methods of contemporary fi ne organic synthesis and underlies quite a number of industrial processes [1-3]. The creation of effi cient catalytic systems proceeding from available complexes of transition metals is the common strategy in this fi eld. Nowadays a dynamic development is observed, and in many cases a signifi cant progress is achieved for catalytic reactions involving quite a number of heteroatoms and elements (B, Si, O, N, S, Se etc.) [1][2][3][4][5][6][7].Notwithstanding the advances in this field, the situation in the investigations of addition to alkynes of molecules containing the phosphorus(V)-hydrogen bond is not clear. The products of the addition along Markownikoff rule were shown to be available in the presence of palladium and nickel catalyst as was reported by Tanaka [8-12], Han [13, 14], Montchamp [15-17], Toffano [18] and in our publications [19][20][21].The accumulated array of the experimental data does not form a general unambiguous pattern, and in some cases the results from various studies are contradictory.The following key problems can be revealed requiring keen attention and deep comprehension: (1)What is the effi cience of catalysts based on palladium and nickel complexes in the addition of the P(V)-H bond to alkynes;(2)What is the reason of the signifi cant difference in the activity of catalyst precursors containing bivalent and zero-valent metal compounds, M(II) and M(0); (3)Why the regioselectivity of addition reactions changes if all of them occur by the alkyne insertion into the metal-phosphorus bond; (4) Ambiguous results exist on the ligand and acid effect. In this report we make the fi rst attempt to understand the reason of some among these contradictions and to suggest the optimum strategy of the studies for their solution.The investigation of catalytic activity of nickel and palladium complexes was carried out on a selected model hydrophosphorylation reaction of 1-heptyne (Scheme 1). It should be stated that similar model systems involving a terminal alkyne without substituents (1-hexyne, 1-hep-

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supporting

confidence: 65%

Section: The Comparison Of Addition Of Molecules Possessing P(v)-h Bondmentioning

confidence: 96%

The comparison of addition of molecules possessing P(V)-H bond to alkynes catalyzed with Pd and Ni complexes

2010

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“…. 113 In addition, examples can be found of Markovnikov-type addition of diphenylphosphine oxide to terminal alkynes catalyzed by Pd(OAc) 2 (5 mol%) and 1,2-bis(diphenylphosphino)ethane (dppe, 8 mol%) in propionitrile as solvent at 100 ºC, 114 as well as the use of a diphosphine-hydrosilane binary systems that allows the regioselective synthesis of branched vinylphosphine oxides from terminal alkynes under Pd(PPh 3 ) 4 catalysis (5 mol%). 115 Moreover, tetraphenyldiphosphine has been used in the hydrophosphinylation reaction of terminal alkynes catalyzed by Pd(OAc) 2 (5 mol%), leading to branched vinylated phosphine oxides after air-oxidation during work-up, 116 and diphenylphosphine oxide has been used in a double addition to oct-1-yne using a Zr (or Hf)-Pd heterobinuclear system as catalyst, the preliminary branched and linear vinylated phosphine oxides being intermediates.…”

Section: Vinyl Phosphines Phosphine Oxides Phosphinates and Phosphomentioning

confidence: 99%

Chemicals from Alkynes with Palladium Catalysts

2013

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“…Addition of diphenylphospholane oxide 6 to terminal alkynes was catalyzed by Pd(PPh 3 ) 4 [13]. Although no mechanism was proposed, the Pd(Me-DuPhos)-catalyzed asymmetric hydrophosphination of an alkyne with a phosphine-borane under kinetic resolution conditions (Scheme 6) presumably involves similar insertion and reductive elimination steps [14].…”

Section: Alkynesmentioning

confidence: 98%

Recent Advances in Metal-Catalyzed C–P Bond Formation

Glueck

2010

C-X Bond Formation

161

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This chapter describes recent advances in metal-catalyzed C-P bond formation, which may be classified into two types of reactions. In hydrophosphination and related processes, P-H groups add across unsaturated C-X (X ¼ C, N, O) bonds. Phosphination of electrophiles typically results in substitution at sp 2 or sp 3 carbon; the P-H group is removed, often by a base. The scope of both nucleophilic and electrophilic partners in these processes is surveyed, and the proposed mechanisms and intermediates in the metal-catalyzed reactions are described.

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Regioselective Metal‐Catalyzed Hydrophosphinylation of Alkynes: Synthesis of Enantiopure α‐ or β‐Substituted Vinylphosphane Oxides

Cited by 30 publications

References 37 publications

The comparison of addition of molecules possessing P(V)-H bond to alkynes catalyzed with Pd and Ni complexes

The comparison of addition of molecules possessing P(V)-H bond to alkynes catalyzed with Pd and Ni complexes

Chemicals from Alkynes with Palladium Catalysts

Recent Advances in Metal-Catalyzed C–P Bond Formation

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