40181-00-8Relevant academic research and scientific papers
The first one-pot metathesis-hydroformylation procedure: a straight synthesis of 2-arylpropanals from renewable 1-propenylbenzenes
Avenda?o Villarreal, Jesus Alberto,Delolo, Fábio Godoy,Granato, Artur Vicari,Gusevskaya, Elena Vitalievna,dos Santos, Eduardo Nicolau
, p. 8007 - 8013 (2021/12/27)
Hydroformylation is a consolidated synthetic tool in the chemical industry, both in commodity and in the fine chemicals industry. Olefin metathesis has been largely employed in the petrochemical sector, and, more recently, in the synthesis of specialty chemicals. Although these reactions may be involved in the same synthetic route for various industrial chemicals, to the best of our knowledge, they have never been combined in a one-pot procedure. As a proof of concept, we have demonstrated in the present work that the ruthenium-catalyzed ethenolysis of renewable 1-propenylbenzenes followed by the rhodium-catalyzed hydroformylation of functionalized styrenes formed in the first step could be done in one pot. The integration of these reactions was not straightforward once the catalyst of the first step interfered with the catalyst of the second step. Under optimized conditions, it was possible to synthesize 2-arylpropanals, a class of compounds valuable as synthetic intermediates to access non-steroidal anti-inflammatory drugs, in overall yields of 85-90%, at low catalyst loadings.
Copper-catalyzed hydroformylation and hydroxymethylation of styrenes
Franke, Robert,Geng, Hui-Qing,Meyer, Tim,Wu, Xiao-Feng
, p. 14937 - 14943 (2021/12/02)
Hydroformylation catalyzed by transition metals is one of the most important homogeneously catalyzed reactions in industrial organic chemistry. Millions of tons of aldehydes and related chemicals are produced by this transformation annually. However, most of the applied procedures use rhodium catalysts. In the procedure described here, a copper-catalyzed hydroformylation of alkenes has been realized. Remarkably, by using a different copper precursor, the aldehydes obtained can be further hydrogenated to give the corresponding alcohols under the same conditions, formally named as hydroxymethylation of alkenes. Under pressure of syngas, various aldehydes and alcohols can be produced from alkenes with copper as the only catalyst, in excellent regioselectivity. Additionally, an all-carbon quaternary center containing ethers and formates can be synthesized as well with the addition of unactivated alkyl halides. A possible reaction pathway is proposed based on our results. This journal is
Chemoenzymatic Cascades toward Methylated Tetrahydroprotoberberine and Protoberberine Alkaloids
Broomfield, Joseph,Hailes, Helen C.,Keep, Nicholas H.,Roddan, Rebecca,Subrizi, Fabiana,Ward, John M.
supporting information, p. 6342 - 6347 (2021/08/30)
Tetrahydroprotoberberine and protoberberine alkaloids are a group of biologically active natural products with complex molecular scaffolds. Isolation from plants is challenging and stereoselective synthetic routes, particularly of methylated compounds are
Synthesis of rac-ɑ-aryl propionaldehydes via branched-selective hydroformylation of terminal arylalkenes using water-soluble Rh-PNP catalyst
Chen, Fen-Er,Gao, Peng,Ke, Miaolin,Liang, Guanfeng,Ru, Tong
, (2021/08/26)
This work detailed the preparation of a class of water-soluble PNP ligands that differed by the nature of the substitute on phenyl ring of ligands. These ligands were incorporated into water-soluble rhodium-PNP complex catalysts that were used to regioselective hydroformylation of a series of terminal arylalkenes, providing efficient access to rac-α-aryl propionaldehydes in good to excellent yield (up to 97%) and branched-regioselectivity (up to 40:1 b/l ratio). Furthermore, gram-scale and diverse synthetic transformation demonstrated synthetic application of this methodology for non-steroidal antiinflammatory drugs.
Pummerer Cyclization Revisited: Unraveling of Acyl Oxonium Ion and Vinyl Sulfide Pathways
Li, Xin,Carter, Rich G.
supporting information, p. 5541 - 5545 (2018/09/25)
Two viable pathways (vinyl sulfide and acyl oxonium ion) for the Pummerer cyclization have been unraveled that expand the reaction scope and capabilities. Use of Br?nsted-enhanced Lewis acidity was key to realization of the vinyl sulfide pathway, whereas selective complexation of the sulfur lone pair facilitated the unprecedented acyl oxonium ion pathway. Preliminary mechanistic investigations support these hypotheses. A range of substrates have been explored to understand the reaction parameters.
Reaction of azides and enolisable aldehydes under the catalysis of organic bases and: Cinchona based quaternary ammonium salts
Destro, Dario,Sanchez, Sandra,Cortigiani, Mauro,Adamo, Mauro F. A.
supporting information, p. 5227 - 5235 (2017/07/11)
Herein we report a two-step sequence for the preparation of amides starting from azides and enolisable aldehydes. The reaction proceeded via the formation of triazoline intermediates that were converted into amides via Lewis acid catalysis. Preliminary st
Hypervalent Iodine(III)-Mediated Cascade Cyclization of Propargylguanidines and Total Syntheses of Kealiinine B and C
Tian, Guilong,Fedoseev, Pavel,Van der Eycken, Erik V.
supporting information, p. 5224 - 5227 (2017/04/24)
An oxidative cascade cyclization of propargylguanidines promoted by phenyliodonium diacetate (PIDA) was developed. The protocol provides an efficient route for the synthesis of the alkaloids kealiinines B and C as well as homologues. The difference in the electronic nature of the acetylene substituent resulted in two ways of the cyclization. A plausible mechanism is proposed based on the experimental results.
NOVEL COMPOUND OR PHARMACEUTICALLY ACCEPTABLE SALT THEREOF, AND PHARMACEUTICAL COMPOSITION CONTAINING SAME AS ACTIVE INGREDIENT
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Paragraph 0219; 0220, (2015/07/15)
The present invention relates to a compound inhibiting Hsp90 and a pharmaceutical composition comprising the same as an active ingredient. The compounds represented by formula 1 and formula 2 of the present invention suppress the expression of Hsp90 so that they can inhibit the accumulation of HIF-1α, the Hsp90 client protein, and also efficiently inhibit the activation of VEGF. In addition, these compounds display low cytotoxicity, so that they can be effectively used as an active ingredient of an anti-cancer agent, a diabetic retinopathy treating agent, and an anti-arthritic agent.
NOVEL COMPOUND OR PHARMACEUTICALLY ACCEPTABLE SALT THEREOF, AND PHARMACEUTICAL COMPOSITION CONTAINING SAME AS ACTIVE INGREDIENT
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Paragraph 0118-0123, (2015/05/26)
The present invention relates to a novel compound inhibiting Hsp 90 and to a pharmaceutical composition including same as an active ingredient. Compounds of formula 1 and formula 2 according to the present invention inhibit the accumulation of HIF-1α protein, which is an Hsp90 client protein, by suppressing Hsp90 expression, and effectively inhibit the activity of vascular endothelial growth factor (VEGF). Furthermore, said compounds have low cytotoxicity and can thus be used as an active ingredient for the treatment of diabetic retinopathy and arthritis.
Flow Chemistry Syntheses of Styrenes, Unsymmetrical Stilbenes and Branched Aldehydes
Bourne, Samuel L.,O'Brien, Matthew,Kasinathan, Sivarajan,Koos, Peter,Tolstoy, Paeivi,Hu, Dennis X.,Bates, Roderick W.,Martin, Benjamin,Schenkel, Berthold,Ley, Steven V.
, p. 159 - 172 (2013/03/13)
Two tandem flow chemistry processes have been developed. A single palladium-catalysed Heck reaction with ethylene gas provides an efficient synthesis for functionalised styrenes. Through further elaboration the catalyst becomes multi-functional and performs a second Heck reaction providing a single continuous process for the synthesis of unsymmetrical stilbenes. In addition, the continuous, rhodium-catalysed, hydroformylation of styrene derivatives with syngas affords branched aldehydes with good selectivity. Incorporation of an in-line aqueous wash and liquid-liquid separation allowed for the ethylene Heck reaction to be telescoped into the hydroformylation step such that a single flow synthesis of branched aldehydes directly from aryl iodides was achieved. The tube-in-tube semi-permeable membrane-based gas reactor and liquid-liquid separator both play an essential role in enabling these telescoped flow processes.
