Hydrophosphination of alkynes and related reactions catalyzed by rare-earth amides

Takaki, Ken; Komeyama, Kimihiro; Kobayashi, Daisuke; Kawabata, Tomonori; Takehira, Katsuomi

doi:10.1016/j.jallcom.2004.11.088

Cited by 31 publications

(17 citation statements)

References 10 publications

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“…Hydrophosphination has been well‐developed for activated substrates, particularly electron‐deficient alkenes, but unactivated substrates remain underrepresented in hydrophosphination ,,. Indeed, the most successful asymmetric hydrophosphination catalysis occurs with activated alkene substrates .…”

Section: Substratesmentioning

confidence: 99%

Challenges in Catalytic Hydrophosphination

Bange

Waterman

2016

Chemistry A European J

145

127

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Despite significant advances, metal-catalyzed hydrophosphination has ample room for discovery, growth, and development. Many of the key successes in metal-catalyzed hydrophosphination over the last decade have indicated what is needed and what is yet to come. Reactivity that is absent from the literature also speaks to the challenges in catalytic hydrophosphination. This Concept article discusses and highlights recent developments that address the ongoing challenges, and identifies areas in metal-catalyzed hydrophosphination that are underdeveloped. Advances in product selectivity, catalyst design, and both unsaturated and phosphine substrates illustrate the ongoing development of the field. Like all catalytic transformations, the benefits are realized through catalyst, ligand, and conditions, and consideration of those features are the route to a yet more efficient and broadly applicable reaction.

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Section: Substratesmentioning

confidence: 99%

Challenges in Catalytic Hydrophosphination

Bange

Waterman

2016

Chemistry A European J

145

127

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“…Scheme ) 5. Lanthanide‐ or calcium‐catalyzed hydrophosphination of alkynes and alkenes,6–8 which involve the insertion of an unsaturated substrate into the metal–phosphorus bond of a phosphido intermediate (Scheme ), include the only examples of metal‐mediated hydrophosphination of simple alkenes 7b. 8 Our results point to an alternative mechanism for hydrophosphination catalyzed by late‐metals that will allow the incorporation of a much wider range of alkene substrates (electron rich and electron deficient) than are currently viable in this transition metal mediated process 9…”

Section: Methodsmentioning

confidence: 99%

Concerted [2+2] Cycloaddition of Alkenes to a Ruthenium–Phosphorus Double Bond

Derrah¹,

Pantazis²,

McDonald³

et al. 2010

Angewandte Chemie

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We recently described a terminal phosphido complex of ruthenium containing a Ru = PR 2 p bond, and demonstrated its high activity in 1,2-addition reactions of polar and nonpolar substrates. [1] Herein we report the [2+2] cycloaddition reactions of this planar phosphido complex with both activated and simple alkenes to yield metallaphosphacyclobutanes, and we provide evidence for a concerted cycloaddition pathway in these P À C bond-forming reactions (Scheme 1 a). Metal-mediated PÀC bond-forming reactions represent a direct and potentially stereoselective route to useful ligands or reagents, [2] but the development and understanding of metal-catalyzed phosphination and hydrophosphination by primary or secondary phosphines lags behind that of the corresponding amination chemistry. [3] Among late-metal examples of such catalysis, the critical P À C bond-forming step has been attributed either to nucleophilic attack of free phosphine onto an unsaturated substrate that has been activated through binding with the metal (e.g. Scheme 1 b), [4] or to attack of the strongly nucleophilic P of a phosphido intermediate (M À PR 2 ) onto a substrate containing an electrophilic carbon atom (e.g. Scheme 1 c). [5] Lanthanideor calcium-catalyzed hydrophosphination of alkynes and alkenes, [6][7][8] which involve the insertion of an unsaturated substrate into the metal-phosphorus bond of a phosphido intermediate (Scheme 1 d), include the only examples of metal-mediated hydrophosphination of simple alkenes. [7b, 8] Our results point to an alternative mechanism for hydrophosphination catalyzed by late-metals that will allow the incorporation of a much wider range of alkene substrates (electron rich and electron deficient) than are currently viable in this transition metal mediated process. [9] The five-coordinate half-sandwich complex [Ru(h 5indenyl)(PR 2 )(PPh 3 )] (1 a,b) reacts rapidly with acrylonitrile to give two isomers of the metallacyclic product 2 a,b, in which the nitrile group on the ruthenium-bound a-carbon atom is oriented either syn or anti with respect to the Ru-indenyl bond (Scheme 2). In solution, these complexes show diagnostic upfield 31 P{ 1 H} NMR signals due to the phosphorus atom in the metallacycle (e.g., syn-2 a: d = À13.3 ppm), and upfield 13 C{ 1 H} NMR signals for the a-carbon atom attached to Ru (e.g., syn-2 a: d = À28.3 ppm). 13 C{ 1 H}DEPT-135 NMR analysis of a mixture of syn-and anti-2 a confirmed their identical regiochemistry, showing that the a-carbon atom in both isomers (d = À29.1 ppm in 13 C NMR spectrum for anti-2 a) contains one proton and not two. Unequivocal assignment of the stereochemistry of syn-2 b was obtained from solution NMR studies of a purified sample, which allowed identification of the signal resulting from the lone proton on the a-carbon atom, and showed its proximity to the PPh 3 aryl protons.[10] X-ray crystallography confirmed the analogous syn structure of the major isomer of 2 a in the solid state ( Figure 1). [11] We detected no trace of the other regioisomers Scheme 1. ...

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“…Takaki et al mentioned an interesting silylphosphination of alkynes and isoprene catalyzed by a Yb‐complex (Fig. 10 (c)) 33…”

Section: Catalytic Activation Of Silylphosphinesmentioning

confidence: 99%

Organophosphine syntheses via activation of the phosphorus‐silicon bond of silylphosphines

Hayashi

2009

The Chemical Record

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This paper describes the recent advances in the syntheses of organophosphines by forming several types of phosphorus-carbon bonds via activation of the phosphorus-silicon bond of silylphosphines. In this account, the activation methods are classified into three types: nucleophile-induced activations, reactions with Lewis acid-activated electrophiles, and transition metal catalyzed reactions. Nucleophile-induced activations of silylphosphines, especially by a fluoride, generated a reactive phosphide equivalent for selective formation of a P-C bond. Silylphosphines also reacted selectively with Lewis acid-activated electrophiles. The Lewis acid mediated/catalyzed additions and substitutions, to form sp3-carbon-phosphorus bonds including an asymmetric reaction, are described. Several important types of transition metal catalyzed reactions of silylphosphines are also mentioned in this account. Selective formation of a P-C bond is achieved through these activations to produce a variety of functional organophosphines including optically active ones.

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Hydrophosphination of alkynes and related reactions catalyzed by rare-earth amides

Cited by 31 publications

References 10 publications

Challenges in Catalytic Hydrophosphination

Challenges in Catalytic Hydrophosphination

Concerted [2+2] Cycloaddition of Alkenes to a Ruthenium–Phosphorus Double Bond

Organophosphine syntheses via activation of the phosphorus‐silicon bond of silylphosphines

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