Pauson-Khand reaction alkynes/allenes

Cyclopropene can also be used as the aUcene component and affords bicyclo[3.1.0]hexen-2-ones upon reaction with alkyne dicobalt octacarbonyl complexes in the presence of NMO (Scheme 250). Vinyl ethers and vinyl esters serve as ethene equivalents in Pauson-Khand reactions. For example, reaction of vinyl benzoate with complex (169) furnished cyclopentenone (170) (Scheme 251). This reaction was used in a synthesis of (-l-)-taylorine and nortaylorine. Allenes participate in intermolecular Pauson-Khand reactions affording alkylidene-substituted cyclopentenones (Scheme 252). ... 

This reaction has found its way into organic synthesis fi and is attractive because of its generality and selectivity. In Drummond s synthesis of hydroxymethylacylfulvene,3 0 for example, a Pauson-Khand reaction of the allene-alkyne 446 gave a 69% yield of 447. In this case, molybdenum hexacarbonyl was used. In Takano s synthesis of dendrobine, 448 was treated with dicobalt octacarbonyl and then NMO to give an 89%... 

The Pauson-Khand reaction has also been carried out under different conditions, such as the use of chiral ligands, including PuPHOS, CamPHOS, and camphorsultam the use of aldehydes as the carbon monoxide source > the use of solid-supported cobalt catalyst to enhance purification, such as the dry-state adsorption the use of colloidal cobalt nanoparticle and the use of metallic cobalt supported on mesoporous silica prepared by decomposing Co2(CO)8 on mesoporous silica supports (SBA-15 and MCM-41) in the refluxing toluene solution.Other modifications include different promoting methods, such as photo-irradiation, microwave irradiation, molecular sieves, TEMPO,A-oxides, and supercritical fluids. Furthermore, the cycloaddition between allene and carbon monoxide under similar conditions is known as the allenic Pauson-Khand reaction,27,41 jjjg reaction among alkyne, carbodiimide, and CO is referred to as the aza-Pauson-Khand reaction. ... 

A rhodium-catalysed Pauson-Khand reaction of an allenic alkyne 7.60 was employed to form the cyclopentenone ring of Achalensolide 7.65, a guaianolide natural product (Scheme 7.18). The butenolide ring was then constructed by free radical chemistry. 

Intramolecular allene alkyne cyclizations using cobalt complexes are nonspecific and both double bonds of the allene participate in the reaction affording [4.3.0] and [3.3.0]ring systems (Scheme 260). Both inter- and intramolecnlar Pauson - Khand-type reactions have been reported using... 

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