Carbonyl Olefination Research Articles

Carbonylation of Olefins by Copper or Silver Carbonyl Supported Catalysts at Room Temperature and Atmospheric Pressure.

Copper and silver carbonyl catalysts were supported on ZrO2, ZrO2•SO3, SiO2•Al2O3, isolite and active carbon. Carbonylation of 1-hexene was carried out by using Cu(CO)n+ or Ag(CO)2+ supported catalyst at room temperature and atmospheric pressure to give tert-C7 carboxylic acid in 30-65% yield in batch reactor. The carbonylation of 1-octene was also carried out by using the same catalyst in column reactor, and tert-C9 carboxylic acid was obtained in 17-23% yield at room temperature and atmospheric pressure.

Metal carbonyl cations in strong acids and their catalytic activities

Recent advances on metal carbonyl cations and their catalytic activities are reviewed and discussed in relation to the property of M–CO bonding. In strong acids, the carbonyl cations of monovalent copper, silver and gold catalyze the carbonylation of olefins, alcohols, dienes, diols, aldehydes and saturated hydrocarbons at room temperature and atmospheric pressure to produce tert-alkanoic acids in high yields.

チオアセタールのチタン‐カルベン錯体への変換を利用する新しい有機合成

Recently we found that various titanium-carbene complexes were produced by the desulfurization of thioacetals with the low-valent titanium species Cp2Ti [P (OEO)3] 2. This article deals with their application to organic synthesis including some guiding conceptions of the study. Desulfurization of thioacetals prepared from α, β-unsaturated aldehydes or 1, 3-bis (phenylthio) propene derivatives in the presence of 1-olefins afforded alkenylcyclopropanes. The intermediates of this reaction, vinylcarbene complexes, reacted with carbonyl compounds to afford the Wittig-like olefination products in good yields. The similar carbonyl olefination using various types of thioacetals and orththioformates with carbonyl compounds including carboxylic acid derivatives also produced a variety of olefins. Furthermore the alkylidenetitanocenes formed from saturated thioacetals reacted with organic molecules having a carbon-carbon multiple bond. When they were treated with alkynes, conjugated dienes were produced with high stereoselectivity. The reaction with allyltrialkylsilanes afforded (Z) -γ-substituted allylsilanes via the formation of titanacyclobutane intermediates. We also found the first [2+1] carbenoid insertion reaction of titanium-carbene complexes with trialkylsilanes and related group 14 organometallics.

Selective hydroboration of unconjugated alkynyl ketones and aldehydes

Unconjugated alkynyl ketones and aldehydes are selectively hydroborated to give the corresponding olefinic carbonyl compounds after protonation, or dicarbonyl compounds after oxidation.

Olefin Carbonylation Catalysis with Cationic Palladium Complexes: Selectivity and Possible Intermediates

AbstractPalladium complexes L2PdX2 containing various group Va ligands and weakly coordinating anions are active catalysts for the carbonylation of olefin substrates. These catalytic systems, though gaining significance in industry for the synthesis of polyketones, are normally characterised by a low chemoselectivity. This derives from the numerous possibilities for initiation and termination reactions which lead to different catalytic cycles and from facile multiple alternating insertion reactions of olefins and carbon monoxide. Based on experiments carried out under conditions of low selectivity and on previously published data, the factors involved in the control of the regio‐, chemo‐ and stereoselectivity for those reactions are discussed, taking current ideas and model studies involving the above palladium complexes into consideration.

ChemInform Abstract: A New Gold Catalyst: Formation of Gold(I) Carbonyl, (Au(CO)n)+ (n = 1, 2), in Sulfuric Acid and Its Application to Carbonylation of Olefins.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Molybdenum catalyzed carbonylation of ethylene to propionic acid and anhydride

We have discovered a low pressure and low temperature process for the single step conversion of ethylene and carbon monoxide to either propionic acid or anhydride utilizing surprisingly active, inexpensive Cr group based catalysts which operate at very high rates under low-to-moderate pressures (30–70 atm) and temperatures (150–200°C). Mechanistic investigations of the Mo based process, which is clearly the most active metal of the group, imply that catalysis is initiated by a rate limiting CO dissociation from Mo(CO) 6. This dissociation appears to be followed by a process which ultimately transfers an I atom from EtI to the coordinatively unsaturated Mo(CO) 5, probably via an inner sphere, electron transfer process. Subsequent reaction of the resultant ethyl radical with Mo(CO) 6 probably generates very reactive odd electron Mo species which are capable of rapid catalysis via classical olefin carbonylation mechanisms. This discovery represents the first case of an efficient carbonylation process based on the Cr group metals and a unique method for initiating carbonylation catalysis. A general description of this process and the mechanistic proposal, which is based on detailed kinetics, spectroscopy and model reactions, will be presented.

A New Gold Catalyst: Formation of Gold(I) Carbonyl, [Au(CO)n]+ (n = 1, 2), in Sulfuric Acid and Its Application to Carbonylation of Olefins

A new gold catalyst, [Au(CO)n]+ (n = 1, 2), was synthesized by using a facile method from commercial gold(III) oxide, Au2O3, in concentrated H2SO4, which exhibits high catalytic activity for carbonylation of olefins. The gold monocarbonyl [Au(CO)]+ (1) and dicarbonyl [Au(CO)2]+ (2) cations coexist in H2SO4 solution, the former of which is much more stable than the latter. Both of the carbonyls show IR spectra of νCO (2194, 2208 cm-1) higher than that of free CO (2143 cm-1), indicating nonclassical (σ-only) gold−CO bonding. The gold carbonyl complexes coexisting in the concd H2SO4 solution exhibit a single resonance in the 13C NMR spectrum at 171 ppm at ambient temperature and pressure, reflecting rapid CO exchange between 1 (164 ppm) and 2 (175 ppm). The nonclassical gold(I) carbonyl solution worked as an excellent catalyst, with which olefins reacted with CO to give tert-carboxylic acids in good yields at room temperature and atmospheric pressure. The gold(I) dicarbonyl cation 2 was found to function as ...

New Carbonyl Olefination Using Thioacetals

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTNew Carbonyl Olefination Using ThioacetalsYasuo Horikawa, Mikako Watanabe, Tooru Fujiwara, and Takeshi TakedaView Author Information Department of Applied Chemistry Tokyo University of Agriculture and Technology Koganei, Tokyo 184, Japan Cite this: J. Am. Chem. Soc. 1997, 119, 5, 1127–1128Publication Date (Web):February 5, 1997Publication History Received2 July 1996Published online5 February 1997Published inissue 1 February 1997https://doi.org/10.1021/ja962240dCopyright © 1997 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views2152Altmetric-Citations109LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (158 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Carbonyls,Chemical reactions,Olefination,Reagents,Titanium Get e-Alerts

ChemInform Abstract: Group Transfer Carbonylations: Photoinduced Alkylative Carbonylation of Alkenes Accompanied by Phenylselenenyl Transfer.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Catalytic Triple Carbonylation of Olefins. Enantioselective Synthesis of 2‐Oxoglutarates.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Palladium catalyzed oxidative carbonylation of alkenes by methyl formate

The use of methyl formate instead of methanol-carbon monoxide, in oxidative carbonylation of alkenes catalyzed by the system Pd II Cu and giving in one step olefinic ester, has been investigated. In this reaction methyl formate acts as a source of alkoxy, but an initial partial pressure of CO (up to 4–5 bar) is required in order to obtain the carbonylation products in high yield. However, CO handling can be avoided by an in situ partial decarbonylation of methyl formate catalyzed by lithium methoxide prior to the oxidative carbonylation.

Catalytic triple carbonylation of olefins. Enantioselective synthesis of 2-oxoglutarates

A new carbonylation reaction, namely “triple carbonylation” of olefins catalysed by cationic palladium complexes to substituted 2-oxoglutarates, has been developed. Even though the chemoselectivity is not high, this reaction allows a one-step synthesis of substituted 2-oxoglutarates with fair to excellent enantioselectivity (enantiomeric excess up to 92%). The reaction is completely regioselective for styrene whereas with aliphatic olefins two regioisomers are formed.

Group Transfer Carbonylations: Photoinduced Alkylative Carbonylation of Alkenes Accompanied by Phenylselenenyl Transfer.

The photolysis of methyl alpha-(phenylseleno)acetate (1b) and related compounds in the presence of an alkene and CO leads to acyl selenides 2 via group transfer carbonylation. The mechanism of this three-component coupling reaction involves the addition of a (methoxycarbonyl)methyl radical to an alkene, the trapping of the produced alkyl free radical by CO, and termination of the reaction by a phenylselenenyl group transfer from the starting material.

ChemInform Abstract: Carbonylation of Styrene and Other Olefins to Keto Compounds with Cationic Palladium Complexes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A new synthesis of lactones from tertiary alkenylcarbinols by cobaltcatalyzed photocarbonylation under ambient conditions

In the presence of a Co catalyst, tertiary vinyl-, propenyl-, and allylcarbinols were chelatively cycloadded to carbon monoxide to produce lactones by xanthone-sensitized photoreaction in tetrahydrofuran, under CO at 1 atmosphere and at room temperature. At lower temperatures the isomerization of alkenylcarbinols was suppressed and lactones were obtained with improved selectivity. The photoprocess was facilitated by addition of pyridine or hydrogen and retarded in presence of amines or phosphines. Mechanistic interpretations for the process and the accompanying effects are discussed. Keywords: chelative carbonylation, photocarbonylation, carbonylation of olefins, lactones synthesis from alkenylalcohols.

Stereoselective 1,3-dipolar cycloadditions of nitrile oxides to sugar olefins. Synthesis of acyclic-sugar isoxazoline C-nucleoside analogs

The cycloaddition 1,3-dipolar of nitrile oxides to sugar nitro olefins and α,β-unsaturated carbonyl olefins has been investigated. The reaction is less regioselective that the cycloaddition of diazoalkanes to the same olefins and while nitrile oxides with bulky substituents afford the sterically less hindered cycloadducts, other nitrile oxides yield a mixture of the two possible regioisomers. However, the reactions seem to be highly stereoselective and single diastereomers were obtained in all the cases studied.

Zur Kenntnis der carbonylmethylenierenden Molybdän‐Aluminium‐ und Wolfram‐Aluminium‐μ‐methylen‐Komplexe

Organomolybdenum and Organotungsten Reagents, VI[1]. On the Carbonyl-Methylenating Molybdenum-Aluminium and Tungsten-Aluminium μ-Methylene Complexes MoCl5, MoOCl3(THF)2, MoO2Cl2, (MeO)2MoCl3, (MeO)4MoCl, WOCl3(THF)2, and WOCl4 form carbonyl-methylenating complexes and 1–2 equiv. of CH4 by reacting with 2 equiv. of Me3Al. These thermolabile complexes are prepared in solution and differ in their properties (e.g. ability to transfer mostly more than 1 CH2 unit per Mo or W atom in carbonyl-olefinating processes; high sensitivity to water, no hydroxy ketone affinity) from the carbonyl-olefinating 1,3-dimetallacyclobutanes (M = Mo, W) and are believed to be mono- and bicyclic analogs (e.g. hypothic structures 3, 6–8) of the Tebbe reagent (1), containing Mo-μCH2 Al or W -μCH2 Al groups, respectively. Analogous complexes seem to be produced by treating MoOCl3(THF)2 with 2 Me2Zn or (MeO)2MoCl3 and (MeO)4MoCl with 2 MeMgBr in each case. Unlike the dimeric and, due to a MoMo bond, diamagnetic Mo derivatives (MeO)2MoCl3 and (MeO)4MoCl (according to 1HNMR structure 9 or 10 and 11 or 12, respectively) the complexes obtained by the reactions (MeO)2MoCl3 + 2 Me3Al and (MeO)4MoCl + 2 Me3Al are paramagnetic, indicating the expected absence of a MoMo bond. The 1HNMR spectrum of the reaction mixture obtained by treating the MoVI derivative MoO2Cl2 with 2 Me3Al in THF shows various signals for μCH2 groups, whereas signals of t-CH2 ligands are missing (t = terminal). In analogy to 1 the carbonyl-olefinating activity of the MoAl and WAl reagents is activated by the addition of 2 equiv. of HMPA. Treatment of PhCOCH2NEt2 (19) with {MoO2Cl2 + 2 Me3Al} leads to carbonyl olefination with formation of 20 and also to α-methylation with formation of PhCOCH(Me)-NEt2 (21), pointing to the intermediate formation of a t-CH2Mo ligand. {MoO2Cl2 + 2 Me3Al + 2 HMPA} has found to be the best reagent for the carbonyl olefination of aldehydes, whereas {WOCl3(THF)2 + 2 Me3Al + 2 HMPA} was optimal for ketones. In 1:1 reactions both reagents normally give better yields than the Tebbe reagent. By applying (WOCl3(THF)2 + 2 Me3Al} and {MoO2Cl2 + 2 Me3Al} on ketones 16–18 an interesting neighbour group effect of electron donor atoms in the δ position to the keto group was observed.

ChemInform Abstract: Synthesis of Cycloalkenes via Alkylidene‐Mediated Olefin Metathesis and Carbonyl Olefination.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Catalytic hydrogenation reactions by [(itcis)-[Ru(6,6′-Cl 2bpy) 2](OH 2) 2] (CF 3SO 3) 2 in biphasic [media (6,6′-Cl 2bpy = 6,6′-dichloro-2,2′-bipyridine)

The water soluble ruthenium complex cis-[Ru(6,6′-Cl 2bpy) 2(OH 2) 2] (CF 3SO 3) 2, (6,6′-Cl 2bpy = 6,6′-dichloro-2,2′-bipyridine) 1 was found to be an effective catalyst for the hydrogenation of organic carbonyl compounds and olefins in biphasic aqueous/organic systems. The catalyst could be reused after simple decantation. Complex 1 was capable of catalysing the H/D exchange reaction between H 2 and D 2O. Incorporation of deuterium into the hydrogenation product of acetophenone was observed in catalysis performed in a D 2O/cyclohexane biphasic medium. A mechanism for the hydrogenation reaction in biphasic media is proposed. It is suggested that an η 2-dihydrogen complex of ruthenium has been formed during the catalysis and that its deprotonation to generate the metal hydride is the crucial step.