Ruthenium-catalyzed Allylation Research Articles

A Ruthenium-Catalyzed C–H Activation Strategy as an Efficient Shortcut in the Total Synthesis of 6,8-Dimethoxy-1,3-dimethyl­isoquinoline

A short and convenient total synthesis of 6,8-dimethoxy-1,3-dimethylisoquinoline, employing a C–H activation/alkenylation strategy, is reported. The approach involves the CeCl3·7H2O-promoted methoximation of 2,4-dimethoxyacetophenone and a methoxime-directed ruthenium-catalyzed allylation. This was followed by a one-pot, ruthenium-catalyzed allyl to propenyl isomerization and a microwave-assisted 6π-azaelectrocylization to complete the sequence. This approach, which entails a shortcut in the synthetic management of the three-carbon side chain, is an improved and more efficient route toward the natural product, which facilitated its access in just three steps and 27.3% overall yield.

Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction.

The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.

Application of a Ruthenium-Catalyzed Allylation–Cycloisomerization Cascade to the Synthesis of (±)-Herbindole A

A short and efficient total synthesis of the cytotoxic cyclopent[<i>g</i>]indole alkaloid (±)-herbindole A from dihydromesitylene has been achieved by incorporating a ruthenium-catalyzed allylation–cycloisomerization cascade reaction as the key step. The protocol has also been applied to the synthesis of the unnatural <i>trans</i>-epimer of the marine natural product.

Catalytic, nucleophilic allylation of aldehydes with 2-substituted allylic acetates: carbon-carbon bond formation driven by the water-gas shift reaction.

The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO2-t-Bu, COMe, Ph, CH(OEt)2, and Me) undergo high-yielding additions with aromatic, α,β-unsaturated, and aliphatic aldehydes. The conditions of the reaction were found to be mild (75 °C, 24-48 h) and only required the use of 2-3 mol % of the triruthenium dodecacarbonyl catalyst under 40-80 psi of CO. The stoichiometries of water and allylic acetate employed were found to be critical to reaction efficiency.

Methyl Ricinoleate as Platform Chemical for Simultaneous Production of Fine Chemicals and Polymer Precursors

The modification of methyl ricinoleate by etherification of the hydroxyl group was accomplished by using a nonclassical ruthenium-catalyzed allylation reaction and also by esterification. Methyl ricinoleate derivatives were engaged in ring-closing metathesis (RCM) reactions leading to biosourced 3,6-dihydropyran and α,β-unsaturated lactone derivatives with concomitant production of polymer precursors. Sequential RCM/hydrogenation and RCM/cross-metathesis were also implemented as a straightforward method for the synthesis of tetrahydropyran and lactone derivatives as well as valuable monomers (i.e., polyamide precursors).

ChemInform Abstract: Ruthenium-Catalyzed Allylation of Primary Alcohols by Allylic Acetates: A Novel Synthesis of α,β-Unsaturated Ketones.

ChemInform Abstract: Ruthenium-Catalyzed Allylation of Primary Alcohols by Allylic Acetates: A Novel Synthesis of α,β-Unsaturated Ketones.

New 1,2,4,5-tetrakis-( N-imidazoliniummethyl)benzene and 1,2,4,5-tetrakis-( N-benzimidazoliummethyl)benzene salts as N-heterocyclic tetracarbene precursors: synthesis and involvement in ruthenium-catalyzed allylation reactions

New tetraimidazolinium and tetrabenzimidazolium salts have been prepared. Upon reaction with t BuOK, they generate carbene ligands, which were associated in situ to [RuCp*(MeCN) 3]PF 6 to produce new ruthenium catalysts that are active for the substitution of allylic substrates by amines, phenols, and carbonucleophiles. The influence of the N-heterocyclic core as well as that of the N-substitutents at the periphery of the salts, on reactivity and regioselectivity have been examined.

Ruthenium-catalyzed allylation reaction in ionic liquid

Ruthenium-catalyzed allylic substitution reactions from unsymmetrical allylic carbonates have been demonstrated to proceed in the ionic liquid 1-hexyl-2,3-dimethylimidazolium hexafluorophosphate ([hdmim][PF 6]) under neutral conditions with very good conversion and regioselectivity, and high level of recyclability of the solvent/catalyst system.

α-Diimines as nitrogen ligands for ruthenium-catalyzed allylation reactions and related (pentamethylcyclopentadienyl) ruthenium complexes

The new Cp*Ru(II) (Cp*: pentamethylcyclopentadienyl) complexes Cp*(dab-R)RuCl, [Cp*(dab-R)(MeCN)Ru][PF 6] (dab-R: RN CH–CH NR; R: iso-propyl, mesityl), and [Cp*(cod)(MeCN)Ru][PF 6], are synthesized in high yields by reacting the corresponding α-diimine or 1,5-cyclooctadiene with [Cp*RuCl] 4 and [Cp*(MeCN) 3Ru][PF 6], respectively. The α-diimine ligands are strongly bonded to the ruthenium centre as shown by the subsequent formation of the alkynyl derivatives Cp*(dab-R)RuC CR′ (R′ = tert-butyl or phenyl) and of the cationic derivatives [Cp*(dab-R)(L)Ru][PF 6] (L = CO, PMe 3). The neutral and cationic α-diimine or 1,5-cyclooctadiene ruthenium complexes are compared as catalyst precursors for the ruthenium-catalyzed allylation of diethyl-sodiomalonate and diethylamine with cinnamyl acetate or ethyl cinnamyl carbonate.

Ruthenium‐Catalyzed Allylation of Aromatic Compounds and Allylic Ether Formation.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Ruthenium-Catalyzed Allylation of Aromatic Compounds and Allylic Ether Formation

Ruthenium-catalyzed allylation of aromatic compounds such as benzene, toluene, p-xylene, anisole, phenol, furans, and thiophenes with allylic alcohol derivatives gives the corresponding allylated products in good to high yields with a high regioselectivity. Only the cationic thiolate-bridged diruthenium(III, III) complexes promote the reaction. Investigation of the allylation pathway in the reaction of cinnamyl alcohol with p-xylene has revealed that it proceeds via two ways: a direct allylation with the alcohol itself and an allylation with dicinnamyl ether formed as an intermediate. A new cationic thiolate-bridged diruthenium(III, IV) complex together with allylated cinnamyl chlorides has been formed in the reaction of the diruthenium(III, III) complex with cinnamyl chloride, this new complex being revealed to be effective as an allylation catalyst. The cationic diruthenium(III, III) complexes can also catalyze the allylation of simple alcohols with allylic alcohols to give the corresponding alkyl ally...

First Ruthenium-Catalyzed Allylation of Thiols Enables the General Synthesis of Allylic Sulfides

First Ruthenium-Catalyzed Allylation of Thiols Enables the General Synthesis of Allylic Sulfides

Ruthenium-catalyzed allylation of primary alcohols by allylic acetates: a novel synthesis of .alpha.,.beta.-unsaturated ketones

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRuthenium-catalyzed allylation of primary alcohols by allylic acetates: a novel synthesis of .alpha.,.beta.-unsaturated ketonesTeruyuki Kondo, Takeshi Mukai, and Yoshihisa WatanabeCite this: J. Org. Chem. 1991, 56, 2, 487–489Publication Date (Print):January 1, 1991Publication History Published online1 May 2002Published inissue 1 January 1991https://doi.org/10.1021/jo00002a003RIGHTS & PERMISSIONSArticle Views696Altmetric-Citations38LEARN 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 PDF (372 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts