143668-01-3

Upstream product

• 35856-38-3 (triisopropyl)silyl cyanide 
• 143633-91-4 diethyl 2-allyl-2-(3-phenylprop-2-yn-1-yl)malonate 
• 591-87-7 Allyl acetate 
• 201230-82-2 carbon monoxide 
• 93006-71-4 2-(3-phenylprop-2-ynyl)malonic acid diethyl ester 
• 104-55-2 3-phenyl-propenal 
• 100-52-7 benzaldehyde 
• 50-00-0 formaldehyd 
• 104-54-1 3-Phenylpropenol 
• 15186-48-8 2,3-isopropylidene-glyceraldehyde 
• 64-18-6 formic acid 
• 189949-44-8 diethyl 3,3a,4,5-tetrahydro-6-(trimethylsilyl)-5-oxopentalene-2,2(1H)-dicarboxylate 
• 755041-73-7 diethyl 3,3a,4,5-tetrahydro-6-iodo-5-oxopentalene-2,2(1H)-dicarboxylate 
• 98-80-6 phenylboronic acid 

Relevant academic research and scientific papers

New insights into the biphasic “CO-free” Pauson-Khand cyclisation reaction through combinedin situspectroscopy and multiple linear regression modelling

“CO-free” carbonylations are catalytic reactions, which strive to replace toxic synthesis gas with less harmful surrogate molecules like formaldehyde. This study sheds light on the mechanism of the biphasic, Rh-catalysed Pauson-Khand type cyclisation reaction by applyingin situRaman spectroscopy together with NMR, dynamic light scattering measurements, and quantum chemical calculations. The reaction is particularly challenging to analyse as the Rh-catalyst features different ligands in the aqueous and organic phase. To tackle this challenge, a novel approach was designed, couplingin situRaman spectroscopy with an advanced data analysis model in the form of multiple linear regression. This fruitful combination of highly specific vibrational spectroscopy with state-of-the-art data analysis allowed not only identification of a new reaction mechanism, but also identification of parameters to accelerate the “CO-free” Pauson-Khand cyclisation,i.e.using mononuclear Rh-phosphine complexes with labile ligands, small organic micelles formed by an increased surfactant concentration, low formaldehyde concentration, and elevated temperature. This novel knowledge-driven optimisation protocol is superior to simple qualitative optimization routines and can be transferred to other reactions and spectroscopy techniques.

Rhodium(i)-catalyzed Pauson-Khand-type reaction using formic acid as a CO surrogate: An alternative approach for indirect CO2 utilization

Formic acid is found to be an ideal CO surrogate for the rhodium(i)-catalyzed Pauson-Khand-type (PK-type) reaction of various substituted 1,6-enynes to afford bicyclic cyclopentenones in moderate to good yields. High TON value of up to 263 and good results in the gram-scale experiment were also obtained, demonstrating the efficacy of this methodology. In addition, heterocyclic molecules of pharmaceutical importance were also furnished via inter- or intra-molecular hetero-PK-type reactions, further broadening the application of current strategy. In this protocol, formic acid was utilized as a bridging molecule for the conversion of CO2 to CO, since formic acid is manufactured via catalytic hydrogenation of CO2 and releases CO in the presence of acetic anhydride readily. Therefore, this methodology represents a green and indirect approach for chemical valorization of CO2 in the preparation of value-added compounds.

Integration of co2 reduction with subsequent carbonylation: Towards extending chemical utilization of co2

Currently, it still remains a challenge to amplify the spectrum of chemical fixation of CO2, although enormous progress has been achieved in this field. In view of the widespread applications of CO in a myriad of industrial carbonylation processes, an alternative strategy is proposed in which CO2 reduction to CO is combined with carbonylation with CO generated ex situ, which affords efficiently pharmaceutically and agrochemically attractive molecules. As such, CO2 in this study was efficiently reduced by triphenysilane using CsF to CO in a sealed two-chamber reactor. Subsequently, palladium-catalyzed aminocar-bonylation, carbonylative Sonogashira coupling of aryl iodides, and rhodium(I)-mediated Pauson–Khand-type reaction proceeded smoothly to yield amides, alkynones, and bicyclic cy-clopentenones, respectively. Furthermore, the formed alkynones can further be successfully converted to a series of heterocycles, for example, pyrazoles, 3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one derivatives and pyrimidines in moderate yields. The striking features of this protocol include operational simplicity, high efficiency, and relatively broad application scope, which represents an alternative avenue for CO2 transformation.

Glycerol - A non-innocent solvent for Rh-catalysed Pauson-Khand carbocyclisations

Rh-catalysed carbocyclisations of the 1,6-enynes 1-8 efficiently gave bicyclo[3.3.0]octenones in neat glycerol. Unexpectedly, ligand-free [Rh(μ-OMe)(cod)]2 was highly selective. Moreover, TPPTS [tris(3-sulfonatophenyl)phosphane trisodium salt]

Rh(I)-catalyzed cyclocarbonylation of enynes with glyceraldehyde: An available carbonyl source derived from sugar alcohols

Catalytic cyclocarbonylation reactions using a glyceraldehyde derivative as a carbonyl source are described. The rhodium(I)-catalyzed reaction of enynes with glyceraldehyde acetonide gave bicyclic cyclopentenones as the products. This presents an interesting use of a sugar alcohol derived carbon resource as well as a convenient procedure for the cyclocarbonylation of enynes. Georg Thieme Verlag Stuttgart · New York.

Cobalt oxide supported gold nanoparticles as a stable and readily-prepared precursor for the in situ generation of cobalt carbonyl like species

A treatment of cobalt oxide supported gold nanoparticles (Au/Co 3O4) under syngas atmosphere effectively generated a cobalt carbonyl-like active species in the reaction vessel. The preparation of Au/Co3O4 was quite simple and the in situ generated cobalt species could be used as a stable and easy handling alternative for dicobalt octacarbonyl without bothersome purification prior to use. The reactions, which are sensitive to the purity of the dicobalt octacarbonyl, such as the alkoxycarbonylation of epoxides and the Pauson-Khand reaction, smoothly progressed with Au/Co3O4.

Rhodium-catalyzed pauson-khand-type reaction using alcohol as a source of carbon monoxide

Three in one pot! Bicyclic cyclopentenones have been synthesized from enynes in alcohol in the presence of a rhodium catalyst through a newly developed auto-tandem catalytic reaction. This process combines three mechanistically distinctive reactions - an

Mild and efficient molybdenum-mediated Pauson-Khand-type reaction

(Chemical Equation Presented) The molybdenum-mediated Pauson-Khand reaction promoted by Mo(CO)3(DMF)3 takes place under very mild conditions in the absence of any promoter. High yields in Pauson-Khand adducts are obtained in the cycl

Inhibition of enone reduction in aqueous-phase Pauson-Khand reactions

NMO-promoted room temperature cyclizations of the cobalt carbonyl complexes of substrates bearing terminal and internal alkynes gave exclusively the Pauson-Khand (PK) reaction adducts in a water-Triton X-100 medium.

Practical and efficient Suzuki-Miyaura cross-coupling of 2-iodocycloenones with arylboronic acids catalyzed by recyclable Pd(0)/C

The first Suzuki-Miyaura cross-coupling of 2-iodocycloenones with arylboronic acids catalyzed by 10% Pd(0)/C is described as an interesting alternative to classical homogeneous conditions. Most of the substrate reacted under mild condition at 25 °C under air in aqueous DME. The conditions described tolerate a wide range of iodoenones and boronic acids. Notably, the procedure features inexpensive reagents and solvents with low toxicity rendering the method environmentally benign. Additionally 10% Pd(0)/C could be recovered and efficiently reused at least five times without significant alteration of the yields of the cross-coupled product.