Recent Advances in Metal-Catalyzed C–P Bond Formation

Abstract

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.

Recent Advances in H-Phosphonate Chemistry. Part 2. Synthesis of C-Phosphonate Derivatives

“…Transition metal-catalyzed formation of the P-C bond is an important method for preparing organophosphorus compounds [16,19,87], thus enabling the synthesis of C(sp 2 )-P derivatives which are not accessible by the Michaelis-Arbuzov [9,10] or Michaelis-Becker [11,12] reactions. Cross couplings promoted by palladium are stereospecific and occur with retention of configuration at the stereogenic phosphorus center [88][89][90].…”

“…This review covers selected, important contributions to H-phosphonate chemistry in the last 5 years (2009-2013) towards C-phosphonate synthesis. Different aspects of H-phosphinate and H-phosphine oxide chemistry have recently been reviewed [17,[19][20][21][22].…”

P-Chirogenic silylphosphine-boranes: synthesis and phospha-Michael reactions

“…10 Usually, the stereoselective synthesis of chiral organophosphorus compounds with P-C bond formation was performed using chlorophosphines or phosphides as electrophilic or nucleophilic reagents, respectively. 9,11 In the last decade, the asymmetric hydrophosphination 12,13 and phospha-Michael addition 14 have also emerged as powerful methodologies for the synthesis of functional derivatives such as chiral organophosphorus compounds, that hold promise for applications in asymmetric catalysis. In this last case, typical reactions of Michael acceptor with free secondary phosphines or their oxide, sulfur or other borane derivatives, were achieved either in basic conditions or by heating.…”

Synthesis of new N-phosphorylated vinylhydropyridines

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It is known that secondary phosphine halides react with electron-deficient acetylenes in the presence of bases [1][2][3][4], radical initiators [1,5, 6], metal complex catalysts [7,8], under microwave irradiation [9], and (rarely) in bulk without any catalyst [10] to form tertiary alkenylphosphine halides and the products of bis-addition.In this work, we performed a three-component reaction of diphenylphosphine sulfide Ia and bis(2-phenylethyl)phosphine selenide Ib with acetylenecarboxylates IIa, IIb and pyridines IIIa, IIIb. The reaction occurred under mild conditions (20-52°C, 1-5 h, MeCN) and led to the regio-and stereoselective formation of (E)-N-ethenyl-1,4-dihydropyridines IVa and IVb with yield of 47 and 17%, respectively.

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“…It is known that secondary phosphine halides react with electron-deficient acetylenes in the presence of bases [1][2][3][4], radical initiators [1,5,6], metal complex catalysts [7,8], under microwave irradiation [9], and (rarely) in bulk without any catalyst [10] to form tertiary alkenylphosphine halides and the products of bis-addition.…”