Triphenylphosphine-catalyzed

Winterfeldt reported a triphenylphosphine-catalyzed lactone formation from benzaldehyde and dimethylacetylenedicarboxylate in less than 20% yield... 

Mechanism for triphenylphosphine-catalyzed phenol-epoxy reaction. 

Phenol-epoxy reaction. See also Epoxy-phenolic reaction entries tertiary amine-catalyzed, 412 triphenylphosphine-catalyzed, 412 Phenol-formaldehyde novolac resin, preparation of, 429... 

Fig. 4. Dissociative mechanism for the rhodium-triphenylphosphine-catalyzed hydroformylation of olefins (24-27).

Fig. 10. Proposed mechanism for the ruthenium-triphenylphosphine-catalyzed hydroformylation of olefins (36).

Debache A, Ghalem W, Boulcina R, Belfaitah A, Rhouati S, Carboni B (2009) An efficient one-step synthesis of 1,4-dihydropyridines via a triphenylphosphine-catalyzed three-component Hantzsch reaction under mild conditions. Tetrahedron Lett 50 5248-5250... 

As shown in Equation (17), 2-trimethylsilyloxyfuran also participated in a triphenylphosphine-catalyzed substitution reaction with Morita-Baylis-Hillman acetates to provide interesting 7-butenolides regio- and diastereoselec-tively <2004AGE6689>. However, the reaction mechanism (vinylogous Michael vs. Diels-Alder) has not been distinguished. 

Palladium-catalyzed phosphination of substituted aryl bromides, using triarylphosphines as the phosphinating agents, has been developed, as illustrated by the synthesis of (57) (Equation (18)).89 This method tolerates various functionalities, e.g., ketone, aldehyde, ester, nitrile, ether, and chloride. Under similar catalytic conditions, various P,/V-ligands, e.g., (58) (Scheme 4), were synthesized using triflate precursors instead.90,91 Arylphosphines can also be prepared by phosphination with triphenylphosphine catalyzed by palladium on charcoal.92... 

Thus, the ester derived from the Lewis acid-catalyzed condensation-fragmentation sequence involving piperonal, cyclopentanone and 1,3-propanediol was readily converted to ethyl 9-(3, 4 -methylenedioxyphenyl)-non-8 -en-2-ynoate by conventional methodology (Scheme 18). This 2-alkynyl ester was then isomerized to the corresponding 2,4-dienoate by the triphenylphosphine-catalyzed internal redox process [35,136]. The 2E,4E- dienoic acid ester served as the immediate precursor of retrofractamide, 50(n=2), the P. nigrum amide 51(n=2), and dehydropipemonaline, 52, all prepared in better than 20% overall yields from piperonal (Scheme 18) [35]. 

Complimenting these [2+2] and [4+2] cycloaddition approaches, is the elegant work of Krische and Jones, who constructed the iridoid core utilizing a (3 + 2) annulation (Scheme 8). Excellent regio- and stereoselectivity were observed for the triphenylphosphine-catalyzed (3 + 2) annulation between enone 36 and butadienoate 37 to yield 38, which was converted to (+)-geniposide (39) in 13 subsequent steps. " ... 

There already exist examples of significant chemical reactions which demonstrate the unusual reaction characteristic resulting from the presence of two metal centers.Here we examine two, neither of which involves phosphine bridging ligands. The autoxidation of triphenylphosphine catalyzed by four-coordinate iron(II) porphyrins in a noncoordinating solvent like toluene occurs by the mechanism shown in Figure Two... 

The oxidation of triphenylphosphine catalyzed by [Pt(PPh3)4] has been extensively studied [87,88,117,118] by Halpem and co-workers who have elucidated many aspects of the reaction mechanism. By the use of optical absorption spectroscopy it has been shown that the predominant species present in a benzene solution of [Pt(PPh3)4] is [Pt(PPh3)3], equation (60). 

Meijer RH, Ligthart GBWL, Meuldijk J, Vekemans JAJM, Hulshof LA, Mills AM, Kooijman H, Spek AL (2004) Triruthenium dodecacarbonyl/triphenylphosphine-catalyzed dehydrogenation of primary and secondary alcohols. Tetrahedron 60 1065-1072... 

One of the most interesting and useful applications of phase transfer catalysis in organometallic chemistry is the catalytic carbonylation reaction of alkyl halides [50]. Palladium tetrakis triphenylphosphine catalyzes the carbonylation of benzyl chloride in a two phase system containing xylene and aqueous sodium hydroxide according to equation 9.21. Phenylacetic acid (4000 moles/mole Pd) is produced in... 

The triphenylphosphine-catalyzed [3+2] cycloaddition reaction of allenyl ketones to cyclic enones affords spirocyclic adducts. For example, from 336 and the allenyl methyl ketone 337 the cycloadducts 338 and 339 (ratio 55 45) are obtained in 84 % yields. Using chiral phosphines, ees of 53-71 % are observed. 

In the triphenylphosphine-catalyzed isomerization, the presence of [PtCl(PPh3)3]Cl could also be detected, suggesting a consecutive displacement mechanism, as in equation (10). No isomerization took place from... 

The triphenylphosphine-catalyzed reaction between allenoates and unsaturated keti-mines affords aza-bicyclo[3,3,0]octane derivatives in good yield with excellent selectivity (Scheme 3.135 and Example 3.19) [145]. These reactions were quite practical since they were operationally trivial to set up, and an assortment of diverse heterocycles were readily accessed using this method. 

Sahu, U. S., Bhadam, S. N., Triphenylphosphine Catalyzed Polimerization of Maleic Anhydride, Makromol. Chem. 1982,183,1653. 

The triphenylphosphine-catalyzed reaction of allenyl-diphenylphos-phine oxide with N- and C-nucleophiles gave y-substituted allylphosphine oxides. Scheme 59 shows the outcome of the reaction with phthalimide. " The bisoxide of BINAP was modified by double bromination using NBS in an ionic liquid (hexylmethylimidazolium PFs or Ntfa) (Scheme 60). The resolution of 2,2 -bis(diphenylphosphinoyl)-l,l -binaphthyl was accomplished via an inclusion complex with chiral 2,2 -dihydroxy-l,l -binaphthyl... 

---