Rhodium(i)-catalysed conjugate phosphination of cyclic α,β-unsaturated ketones with silylphosphines as masked phosphinides

Trepohl, Verena T.; Oestreich, Martin

doi:10.1039/b706137d

Cited by 19 publications

(11 citation statements)

References 20 publications

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“…Similar p-allyl intermediates were proposed in Rh-catalyzed conjugate addition of phosphido groups to enones [87][88][89]. Silylphosphine substrates were suggested to generate Rh-phosphido intermediates from a Rh-OH catalyst precursor.…”

Section: Allyl Substratesmentioning

confidence: 95%

Recent Advances in Metal-Catalyzed C–P Bond Formation

Glueck

2010

C-X Bond Formation

159

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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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Section: Allyl Substratesmentioning

confidence: 95%

Recent Advances in Metal-Catalyzed C–P Bond Formation

Glueck

2010

C-X Bond Formation

159

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“…Silylphosphines, having one or more phosphorus‐silicon bond(s), are conveniently prepared through the reaction of a phosphorus nucleophile with a silicon electrophile. Lithium, sodium, and magnesium phosphides prepared in situ could be successfully converted to the corresponding silylphosphines by treatment with adequate chlorosilanes 12–16. Oestreich and co‐workers recently reported that the silylphosphines with a phenyl group on the silicon could not be synthesized by this process: the reversed combination (a silyllithium and a chlorophosphine) afforded the corresponding silylphosphines in good yields 15.…”

Section: Preparation and Properties Of Silylphosphines12mentioning

confidence: 99%

“…12). 15 They proposed that the key to the success of the process is an intramolecular nucleophilic attack of the hydroxy group on the rhodium to the silicon, where the phosphorus‐silicon bond would be weakened to make transmetallation possible. Most of the reported catalytic reactions of silylphosphines are certainly recognized to proceed by a metal‐phosphide formed by transmetallation, where an activation of the phosphorus‐silicon bond is essential.…”

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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“…However, the terminal acetylenes are more reactive than enone toward the alkynyl rhodium intermediate. Thus the terminal acetylene favors dimerization, which results in the predominant formation of acetylene dimers instead of a-alkynylketones (Scheme 179) [322][323][324][325][326][327]. This problem can be solved by the rhodium-catalyzed 1,3-rearrangement of an alkynyl group from alkynyl alkenyl carbinols, while the concentration of the acetylene is maintained during the reaction.…”

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confidence: 96%

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Heravi

Dehghani

Zadsirjan

2016

Tetrahedron: Asymmetry

109

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Rh-catalyzed asymmetric 1,4-addition reactions to a,b-unsaturated carbonyl and related compounds: an update Available online xxxx Dedicated to my son, OMID on the occasion of his 35th birthday. a b s t r a c tThe Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to an appropriate receptor has been a growing area of research over the last decade. The receptors for such a 1,4-addition reaction are chiefly a,b-unsaturated ketones, esters, amides, enones, nitroalkenes, and occasionally phosphonates etc. This reaction in the presence of chiral rhodium complexes introduce the aryl and alkenyl groups at the b-position of the above electron poor olefins, enantioselectively. Chiral Rh complexes similar to other transition metals can be added to some electron poor olefins, in turn making them viable to attack by various organometallic reagents for highly enantioselective C-C bond formation. The Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to electron poor olefins has been reviewed in 2003. Due to the importance of the asymmetric C-C bond formation via 1,4-conjugate addition reactions and the number of such reactions catalyzed by Rh-complexes, in this review we highlight the recent advances in Rh-complex asymmetric catalyzed 1,4-addition reactions since 2003.

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Rhodium(i)-catalysed conjugate phosphination of cyclic α,β-unsaturated ketones with silylphosphines as masked phosphinides

Abstract: Nucleophile-activation of the phosphorus(iii)-silicon linkage in silylphosphines generates a nucleophilic phosphorus(iii) equivalent thereby allowing for a rhodium-catalysed conjugate phosphination of beta-substituted alpha,beta-unsaturated acceptors.

Cited by 19 publications

References 20 publications

Recent Advances in Metal-Catalyzed C–P Bond Formation

Recent Advances in Metal-Catalyzed C–P Bond Formation

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

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

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