Carbonyl coupling reaction

Carbonyl Coupling Reactions (McMurry Reaction) (Smith Ch. 13.7.F)... 

Although analogous to the direct coupling reaction, the catalytic cycle for the carbonylative coupling reaction is distinguished by an insertion of carbon monoxide into the C-Pd bond of complex A (see A—>B, Scheme 31). The transmetalation step-then gives trans complex C which isomerizes to the cis complex D. The ketone product E is revealed after reductive elimination. 

Palladium(0)-catalyzed coupling reactions - i. e. the Heck and Sonogashira reactions, the carbonylative coupling reactions, the Suzuki and Stille cross-coupling reactions, and allylic substitutions (Fig. 11.1) - have enabled the formation of many kinds of carbon-carbon attachments that were previously very difficult to make. These reactions are usually robust and occur in the presence of a wide variety of functional groups. The reactions are, furthermore, autocatalytic (i.e. the substrate regenerates the required oxidation state of the palladium) and a vast number of different ligands can be used to fine-tune the reactivity and selectivity of the reactions. 

Miller PW, Long NJ, de Mello AJ et al (2006) Rapid formation of amides via carbonylative coupling reactions using a microfluidic device. Chem Commun 5 546-548... 

Carbonylative coupling reaction of Ar3Bi and carbon monoxide takes place under rhodium catalysis (Scheme 46) [61, 62]. Ph3Bi reacted with carbon monoxide in the presence of 5 mol% of [RhCl(CO)2]2 in MeCN at room temperature to give benzophenone in 71% yield together with a small amount of biphenyl. The same... 

Scheme 46 Carbonylative coupling reaction of Ar3Bi with carbon monoxide...

A similar carbonylative coupling reaction was applied to the kinetic resolution of secondary alcohols [63]. In the presence of a Pd catalyst ligated by chiral oxazolinylferrocenylphosphine, the pentavalent Ph3Bi(OAc)2 and carbon monoxide effectively benzoylated secondary alcohols, and up to 48% enantiomeric excess (ee) was attained (Scheme 47). Although the enantioselectivity is not satisfactory, this is a unique new procedure for the kinetic resolution. 

Scheme 47 Kinetic resolution of secondary alcohols by carbonylative coupling reaction of Ph3Bi (OAc)2...

Carbonylative coupling reaction, 68, 116 3-Carboxy-5-dodecen-2-one, (E), 68, 210 Carboxylation, vicinal di-, 68, 41 Carboxylic acids, reduction, 66, 160... 

Alkynyl(phenyl)iodonium salts can be effectively used in palladium(O) or copper(I) catalyzed coupling or carbonylative coupling reactions with various organozirconium complexes (Scheme 57) [117-119]. 

K. Tanaka, H. Suzuki, H. Osuga, Non-photochemical Route to Chiral Disub-stituted [7]Thiaheterohelicenes via Biaryl- and Carbonyl-coupling Reactions, J. Org. Chem. 1997, 62, 4465-4470. 

The general catalytic cycle for this carbonylation coupling reaction is analogous to direct carbon-heteroatom coupling [scheme (39)] except that carbon monoxide insertion takes place after the oxidative addition step and prior to the nucleophilic attack of the amine [scheme (40)] ... 

Explain why carbon-heteroatom carbonylative coupling reactions are preferably carried out with palladium-based catalysts give an example of the catalytic cycle in the carbonylative polycondensation of dihaloarene and bisphenol, leading to a polyester. 

J. E. McMurry, Carbonyl-Coupling Reactions Using Low-Valent Titanium, Chem. Rev. 1989, 89,1513-1524. T. Lectka, The McMurry Recation, in Active Metals (A. Fiirstner, Ed.), 85, VCH, Weinheim, Germany, 1996. 

J. E. McMurry, Carbonyl-coupling reactions using low-valent titanium, Chem. Rev. 1989, 89, 1513-1524. 

A prototype example is the famous McMurry coupling of carbonyl compounds to alkenes (Scheme 1) [4]. The very high stability of the accumulating titanium oxides constitutes the thermodynamic sink which drives the conversion but demands the use of stoichiometric or excess amounts of the low-valent titanium reagent [Ti]. Only recently has it been possible to elaborate a procedure that for the first time enables us to perform intramolecular carbonyl coupling reactions catalyzed by titanium species [5]. 

Under an atmospheric pressure of carbon monoxide, aryl- and alkenylsilanes undergo a carbonylative coupling reaction with aryl and alkenyl halides [44,45]. The optimized conditions for arylsilanes involve the use of N,M-dimethyl-2-imidazolidinone (DMI) as a solvent and KF as a fluoride ion source (Eq. 38), whereas alkenylsilanes prefer THF and TBAF (Eq. 39). 

An alternative strategy to prepare ( )-cembrene A (59) by this group is described below. The key step here is a titanium-induced intramolecular carbonyl coupling reaction starting from -geranylacetone and geraniol (137) (Scheme 6-16). ... 

Templeton and co-workers used the alkylidyne-carbonyl coupling reaction shown in Eq. (156) for the synthesis of the asymmetric alkyne com-... 

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