Intramolecular Cyclization of Arylalkynes with C‐O Bond Formation on Ruthenium Complexes

Ma, Hao‐Wei; Chang, Wei‐chen; Tsai, Fu-Yuan; Lin, Ying‐Chih; Huang, Shou‐Ling; Liu, Yihong; Wang, Yu

doi:10.1002/jccs.201300037

Cited by 7 publications

(3 citation statements)

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“…2-Isobenzofurfuryl carbene complexes were isolated from the reactions of CpRe(CO) 3 with o -ArCCC 6 H 4 C(O)Me (Ar = Ph, p -C 6 H 4 OMe,and p -C 6 H 4 CF 3 ), the reactions of CpRuCl(PPh 3 ) 2 /KPF 6 with o -HCCC 6 H 4 C(O)R (R = Me and t Bu), and the reactions of β-ethynyl α,β-unsaturated ketones with Cr(CO) 5 (THF) or W(CO) 5 (NEt 3 ). , Pyranylidene complexes were isolated from the reactions of CpRuCl(PPh 3 ) 2 /KPF 6 with o -HCCC 6 H 4 C(O)R (R = H, Me, and t Bu), and the reactions of M(CO) 5 (L) (M = Cr, Mo, and W; L = THF and NEt 3 ) with β-ethynyl α,β-unsaturated esters or amides and o -ethynylarylketones ( o -HCCC 6 H 4 C(O)R) (R = aryl, alkyl, vinyl, and H) . A vinylidene complex has been isolated from the reaction of CpRuCl(PPh 3 ) 2 /NaPF 6 with o -HCCC 6 H 4 CO 2 Me . A pyrylium complex has been detected in the reaction of W(CO) 5 (THF) with o -HCCC 6 H 4 C(O)Pr (in 5 min.)…”

Section: Resultsmentioning

confidence: 99%

“…Despite the intense interest in catalytic reactions involving these transformations, stoichiometric reactions of ene-yne-carbonyl compounds with metal complexes have been much less studied. Efforts to isolate or detect well-defined 2-furanyl carbene ( D ), pyrylium ( E ), and pyranylidene ( F ) complexes have only been described for reactions of ene-yne-carbonyl compounds with transition metal complexes CpRe(CO) 3 , M(CO) 5 (L) (M = Cr, Mo, and W; L = THF, Et 2 O, and NEt 3 ), − and CpClRu(PPh 3 ) 2 /KPF 6 . The products isolated or observed from these reactions were found to be dependent on substituents of the organic substrates, metals, and even the reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

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Substituent Effect on the Reactions of OsCl₂(PPh₃)₃ with o-Ethynylphenyl Carbonyl Compounds

et al. 2020

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Reactions of OsCl 2 (PPh 3 ) 3 with o-ethynylphenylcarbonyl compounds o-HCCC 6 H 4 C(O)R (2, R = H (a) and Et (b)) produced the η 3 4c), which contains both a vinylidene and a vinyl or isobenzofuranyl carbene ligand. The structural data of 4c suggest that the complex can also be regarded as a metalated isobenzofurfuryl cation. Computational studies indicate that η 3 -oethynylphenyl-carbonyl complexes 3 are kinetically favored products, while complex 4c is a thermodynamically favored product. The substituent effect on the selectivity for the pathways leading to the formation of isomeric η 3 -o-ethynylphenylcarbonyl complex OsCl 2 (PPh 3 ) 2 {η 3 -(o-HCCC 6 H 4 C(O)R)}, 2-isobenzofuranyl carbene OsCl 2 {CH−CC 6 H 4 C(O)R}(PPh 3 ) 2 , pyrylium OsCl 2 {−C(CH)C 6 H 4 C(O)R}(PPh 3 ) 2 , and pyranylidene OsCl 2 {CCHC 6 H 4 C(O)R}(PPh 3 ) 2 from the complexes OsCl 2 (PPh 3 ) 2 {η 2 -(o-HCCC 6 H 4 C(O)R)} (R = H and NEt 2 ) has been investigated computationally.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Substituent Effect on the Reactions of OsCl₂(PPh₃)₃ with o-Ethynylphenyl Carbonyl Compounds

et al. 2020

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“…[25] In 2013, they reported the formation of Ru-isobenzofurylcarbene (2a)a nd Ru-isochromene-carbene( 2b)c omplexes from the reactions between aldehyde/ketone-functionalized phenyla cetylenes S2 and [Cp(PPh 3 ) 2 RuCl] (Scheme 18). [28] Complexes 2a and 2b were rationalized to be resultsof"non-vinylidene-involving" and "vinylidene-involving" pathways, respectively.…”

Section: Catalytic Ru II -Mediated Cyclizations Of N/o-functionalizedmentioning

confidence: 99%

Ruthenium‐Induced Cyclization of Heteroatom‐Functionalized Alkynes: Progress, Challenges and Perspectives

Chung

Yeung

Wong

2020

Chemistry A European J

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Metal-induced cyclization of functionalized alkynes represents one of the most general approaches to prepare organic heterocycles. AlthoughR u II centers are well-established to promote alkyne to vinylidener earrangements and many Ru II -mediated alkyne cyclizations have been rationalized to be the resultso fp ost-vinylidene transformations, recent discoveries indicate that Ru II centers can serve as electrophiles and induce alkyne cyclizationsw ithoutv inylidene intermediacy. In this Minireview,a no verview of the Ru II -induced cyclization of heteroatom-functionalized alkynes in the last decadei sp rovided, with an emphasis on the discoveries and validations of the unconventional "non-vinylidene-involving" pathways. Recent Progress of Ruthenium-Induced Cyclization of AlkynesResearcho nt he activation of heteroatom-functionalizeda lkynes by Ru II complexes for oxygen-and nitrogen-containing heterocycles of different ring sizes (5-to 8-membered) continues unabated. Most reported Ru complexes ares upported by Cp (Cp = cyclopentadienyl) or structurally analogous h 5 -ligands, amine-or mixed amine/phosphine-basedc helates. In general, the catalyst loadings are almost lower than 10 mol %a nd can be as low as 0.5 mol %. Although the cyclizations are mostly demonstrated with terminala lkynes, there are increasing number of successful reports on cyclizing internal alkynes.T he use of proton shuttles( internal or external bases which facilitate protont ransfer) has been found to be critical in many of these catalytic reactions. Noteworthy,s everal recent studies clearly indicatet hat the "vinylidene-involving" and "non-vinylidene-involving" pathwaysd epicted in Scheme 1are competing mechanisms. In this section, Ru-catalyzedc yclization of heteroatom-functionalized alkynes in the last decade is discussed in chronological order,e xcept in the cases of certain serial or outlying works. Catalytic Ru II -mediated cyclizations of N/O-functionalized alkynesthrough "vinylidene-involving" pathwaysThe successful isolations of Fe-, Ru-, and Os-oxacarbene complexesf rom the reactions between homopropargylic/bis-ho-Scheme1.(a) Established mechanisms for the formation of Ru-vinylidene species. (b) Electrophilic cyclizationso fheteroatom-functionalized alkynes induced by Ru.[a] Dr.Scheme8.Ru-catalyzed cycloisomerizations of alkynols into 5-, 6-and 7membered oxacycles developed by Jia and co-workers. [13,14] Scheme7.Ru-catalyzed cyclizationso fa niline-and phenol-tethered alkynes into indoles and benzofurans, respectively developed by Grotjahn and coworkers. [11,12] Scheme9.Ru-catalyzed cycloisomerizations of hydroxyl-and amine-substituteda lkynes into isochromenes, indolesa nd isoquinolinones developedby Blacquiereand co-workers. [15][16][17] Scheme10. Ru-catalyzed cycloisomerizations of alcohol-tethered alkynes developedb yWen and co-workers. [18] Chem.E ur.Scheme20. Isolation of, and proposed formation mechanism for 4a.The synthesis of 4b is also depictedf or reference [31].Scheme21. Isolation of, and proposed formation mechanism for...

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Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities

Chia

Kuo

Huang

et al. 2018

Chemistry An Asian Journal

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Ar emarkable intermolecular dehydrative coupling reaction with the formation of aC ÀCb ond was found for the vinylidenec omplex 2a,y ielding the dinuclear bisvinylidene complex 4a.C omplex 2a containing1 -hydroxyindan moiety wasf irst formed from the reactiono fo-propynyl benzaldehyde 1a with [Ru]-Cl ([Ru] = Cp(PPh 3 ) 2 Ru) by acyclization process. For analogousa ldehyde 1b containing an additional 1,3-dioxolane group on the aryl ring, similari ntermolecular coupling yields the dinuclear bisvinylidene complex 4b.H owever,t he fluoro group on the aryl ring in aldehyde 1c inhibits the coupling reaction, giving only the vinylidene complex 2c.F or the reactions of [Ru]-Cl in MeOH with compounds 1f, 1g and 1h,e ach with ak etone functionality, cyclization gives vinylidenec omplexes 2f,2 gand 2h,r e-spectively.H owever,n os imilari ntermolecular couplingw as observed, instead, the intramolecular dehydration yields 8f, 8g and 8h,r espectively.I nC DCl 3 ,c atalytic cyclization is observedf or the o-propynylphenyl ketone 1h with [Ru]-Cla t 50 8Cg iving the isochromene products 14 h.F urthermore, treatment of the o-propynylaryl a,b-unsaturatedk etones 1k-m and 1n with [Ru]-Cl in MeOH affords the corresponding vinylidene complexes 10 k-m and 11 n each with 1-benzosuberonem oiety in the presence of NH 4 PF 6 .T hese intramolecular cyclization products weref ormed by the addition of Cb onto the terminal carbon of the alkenem oiety.A ll these reactionp roducts were characterized by spectroscopic methods. In addition, structures of complexes 4a,a nd 10 l were confirmed by single crystal X-ray diffraction analysis.Scheme2.Reactions of two o-propynylaryl aldehydes.Scheme3.Proposed mechanism for the formation of 2a and subsequent transformation to 4a.Scheme4.Reactions of 1d and 1e with [Ru]-Cl.Scheme5.Reactions of o-propynylaryl ketone with no a,b-unsaturated olefin.Scheme6.Formation of isochromene 14 h andproposed mechanism.

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Intramolecular Cyclization of Arylalkynes with C‐O Bond Formation on Ruthenium Complexes

Cited by 7 publications

References 69 publications

Substituent Effect on the Reactions of OsCl₂(PPh₃)₃ with o-Ethynylphenyl Carbonyl Compounds

Substituent Effect on the Reactions of OsCl₂(PPh₃)₃ with o-Ethynylphenyl Carbonyl Compounds

Ruthenium‐Induced Cyclization of Heteroatom‐Functionalized Alkynes: Progress, Challenges and Perspectives

Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities

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Intramolecular Cyclization of Arylalkynes with C‐O Bond Formation on Ruthenium Complexes

Cited by 7 publications

References 69 publications

Substituent Effect on the Reactions of OsCl2(PPh3)3 with o-Ethynylphenyl Carbonyl Compounds

Substituent Effect on the Reactions of OsCl2(PPh3)3 with o-Ethynylphenyl Carbonyl Compounds

Ruthenium‐Induced Cyclization of Heteroatom‐Functionalized Alkynes: Progress, Challenges and Perspectives

Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities

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Substituent Effect on the Reactions of OsCl₂(PPh₃)₃ with o-Ethynylphenyl Carbonyl Compounds

Substituent Effect on the Reactions of OsCl₂(PPh₃)₃ with o-Ethynylphenyl Carbonyl Compounds