Pyryliumverbindungen. 41. 7aH-Cyclopenta[b]pyran-7-one durch Ringtransformation von 2,4,6-Triaryl-pyryliumsalzen mit acyclischen 1,2-Diketonen

Pyrylium Compounds. 41. 7aH-Cyclopenta[b]pyran-7-ones by Ring Transformation of 2,4,6-Triarylpyrylium Salts with Acyclic 1,2-Diketones Reaction of 2,4,6-triarylpyrylium salts 1 with acyclic 1,2-diketones 2 (CH₃COCOR, R = Me, Ph) in the presence of an appropriate condensing agent (e.g. piperidine acetate, triethyl-amine/acetic acid, sodium acetate) yields the hitherto unknown 2,4,5,7a-substituted 7aH-cyclopenta[b]pyran-7-ones 3 as a result of a new type of ring transformation (2,5-[C₄O+C]/2,3-[C₂+C₃]). A characteristic feature of compounds 3 is their ability to undergo electrophilic substitutions. Thus, stepwise bromination of the 7a-methyl derivative 3a in acetic acid affords 6-bromo-7a-methyl-2,4,5-triphenyl-cyclopenta[b]pyran-7-one ( 4 ) and 3,6-dibromo-7a-methyl-2,4,5-triphenyl-cyclopenta[b]pyran-7-one ( 5 ); analogously, nitration of 3a leads to 7a-methyl-6-nitro-2,4,5-triphenyl-cyclopenta[b]pyran-7-one ( 6 ), indicating that position 6 is the favoured position for electrophilic substitutions. Contrary to the 3,5-unsubstituted pyrylium salts 1 , the 3,5-dimethyl-2,4,6-triphenyl-pyrylium perchlorate ( 13 ) reacts with 1,2-diketones 2 through a 2,6-[C₅+C] transformation to give arylsubstituted 1,2-diones 14 . The structure of the new compounds was determined by spectroscopic methods and by a single crystal X-ray analysis of the dibromo derivative 5 .     

Ringtransformationen heterocyclischer Verbindungen. XII. Neuartige Spiroindoline via Ringtransformation von 2,4,6-Triaryl-pyryliumsalzen mit 2-Methylen-indolinen

Ring Transformations of Heterocyclic Compounds. XII. Novel Spiroindolines via Ring Transformation of 2,4,6-Triarylpyrylium Salts with 2-Methyleneindolines 2,4,6-Triarylpyrylium salts 1 react with 2-methyleneindolines 2 or their salts 2 HX in the presence of triethylamine/acetic acid in ethanol by a 2,5-[C₄ + C₂] pyrylium ring transformation to give diastereomerically pure 6-aroyl-3,5-diaryl-spiro[cyclohexa-2,4-diene-1,2′-indolines] 3 , which represent a novel type of spiroindoline compounds. When the 1′-phenyl substituted spiroindolines 3 (RPh, R′H) are treated with p-toluenesulfonic acid in chloroform the 4,6-diaryl-2-[1-methyl-1-(2-phenylaminophenyl)methyl]benzophenones 4 are obtained as the result of an intramolecular amine elimination. Structural elucidation of the reaction products 3/4 is based on spectroscopic data and on an X-ray determination of the bis(4-bromophenyl) substituted spiroindoline 3i.     

Ringtransformationen heterocyclischer Verbindungen. VII. 2,4,5-Triaryl-benzophenone aus 2,4,6-Triaryl-pyryliumsalzen und Arylacetaldehyden: Erste Pyryliumringtransformationen mit Aldehyden als Kohlenstoffnucleophile

Ring Transformations of Heterocyclic Compounds. VII. 2,4,5-Triarylbenzophenones from 2,4,6-Triarylpyrylium Salts and Arylacetaldehydes: First Pyrylium Ring Transformations with Aldehydes as Carbon Nucleophiles 2,4,6-Triarylpyrylium salts 1 react with arylacetaldehydes 2 in the presence of sodium acetate in ethanol by a 2,5-[C₄+C₂] ring transformation to give 2,4,5-triarylbenzophenones 3 in high yield. Besides the sodium acetate, sodium methanolate, triethylamine, triethylamine/acetic acid or piperidine acetate can be applied as condensing agent. The reaction represents the first pyrylium ring transformation initiated by aldehydes.     

Pyryliumverbindungen. 30. C-Alkylierung von 1,3,5-Triaryl-penten-1,5-dion-Enolaten: Ein einfacher Zugang zu 3-alkylsubstituierten 2,4,6-Triaryl-pyryliumsalzen

Pyrylium Compounds. 30. C-Alkylation of 1,3,5-Triaryl-pentene-1,5-dione Enolates: A Simple Approach to 3-Alkylsubstituted 2,4,6-Triarylpyrylium Salts 1,3,5-Triaryl-pentene-1,5-dione enolates ( 10 ), obtainable in crystalline form from 2,4,6-triarylpyrylium pseudobases ( 9 ) and sodium methoxide in benzene/ether, react in dipolar aprotonic solvents (e.g. DMSO, DMF) with various types of alkyl iodides to give C-alkylation products ( 11 ) which afford 3-substituted 2,4,6-triarylpyrylium salts ( 12 ) on treatment with perchloric acid. This reaction sequence proved to be a convenient synthetic route to pyrylium salts ( 12 ) having 3-oriented substituents such as normal or branched alkyl groups C_nH_2n+1 (e.g.n = 1–5), isotopically modified alkyl groups (e.g. C[²H₃], C₂[²H₅]), allyl type substituents (e.g. CH₂CHCH₂, MeCHCHCH₂, CH₂, CH₂CMeCH₂) or benzyl groups (e. g. PhCH₂, 4-Br C₆H₄CH₂). Bifunctional alkylating agents (e.g. 1,4-diiodobutane, o-xylylenediiodide) resulted in a novel type of bispyrylium salts ( 14 ) with 3,3′-linkage. The pyrylium salts obtained were characterized by their ¹H-n.m.r. and u.v. spectra as well as, in most cases, by transformation into the corresponding pyridine derivatives ( 13 ) and bispyridines ( 15 ) respectively.     

Pyryliumverbindungen. 38. Zur Ringtransformation von 2,4,6-Triaryl-thiopyryliumsalzen mit Essigsäureanhydrid zu Arylbenzenen und Thiobenzophenonen

Pyrylium Compounds. 38. About the Ring Transformation of 2,4,6-Triarylthiopyrylium Salts by Acetic Acid Anhydride to Arylbenzenes and Thiobenzophenones 2,4,6-Triarylthiopyrylium salts 5 react in the presence of an appropriate condensing agent (sodium acetate, carbonate, methoxide, tert-butoxide or potassium acetate) with acetic acid anhydride to yield arylbenzenes 3 and thiobenzophenones 6 . This ring transformation represents the first example of the conversion of the moiety into the thiocarbonyl group Under the same conditions 3,5-dimethyl-2,4,6-triphenylthiopyrylium perchlorate ( 13 ) forms via [1,5]-sigmatropic rearrangement the thiobenzophenone 15 . The structure of the new compounds 6 was proved by spectroscopic methods as well as by degradation reactions. Thus, hydrogen peroxide converts 6a to the known benzophenone 4 . Alkaline saponification gives the 2-hydroxy-benzophenone 8 , whereas heating with hydrochloric acid causes a selective cleavage of the acetoxy group to the 2-hydroxy-thiobenzophenone 7 .     

Pyryliumverbindungen. 42. Benzocycloalkenone und Dihydro-2H,7H-1-benzopyranone aus 2,4,6-Triaryl-pyryliumsalzen und Cycloalkan-1,2-dionen

Pyrylium Compounds. 42. Benzocycloalkenones and Dihydro-2H,7H-1-benzopyranones from 2,4,6-Triarylpyrylium Salts and Cycloalkane-1,2-diones 2,4,6-Triarylpyrylium salts 1 react with cycloalkane-1,2-diones 2 in the presence of an appropriate condensing agent to yield benzocycloalkenones 3 . Thus, sodium acetate and cyclo-hexane-1,2-dione ( 2a ) lead to the dihydro-2H-naphthalenones 3a – i , whereas with cycloheptane-1,2-dione ( 2b ) and piperidine acetate, triethylamine or sodium acetate the tetrahydro-5H-benzo-cyclohepten-5-ones 3j – r are formed. As shown for the example 3a, j → 4a, b , benzocycloalkenones of type 3 can be converted into phthalazines 4 on heating with hydrazine in ethanol. By reaction of the dione 2a and an equimolar mixture of triethylamine and acetic acid or morpholine acetate with the salts 1 5,6-dihydro-2H,7H-1-benzopyran-8-ones 5 are obtained as a result of a new type of ring transformation. The pyrans 5 can be cleaved with perchloric acid in ethanol to 5,6,7,8-tetrahydro-8-oxo-1-benzopyrylium perchlorates 6 . If the pyrans 5 are heated with sodium acetate in ethanol, a conversion to benzocycloalkenones 3 is achieved (cf. 5a → 3a ). The structure of the new compounds was established by spectroscopic methods.     

Pyryliumverbindungen. XXIII. 2-Dialkylamino-2H-pyrane aus tetra- und pentasubstituierten Pyryliumsalzen

Pyrylium Compounds. XXIII. 2-Dialkylamino-2H-pyrans from Tetra- and Pentasubstituted Pyrylium Salts. Tetra- and pentasubstituted pyrylium salts of type 6 react with secondary alkyl amines to give stable crystalline 2-dialkylamino-2h-pyrans 7 . In the case of tetrasubstituted pyrylium salts 6 , R′ = Me, R″ = H the reaction occurs regioselectively leading to 2H-pyrans with Me at C-3 of the heterocyclic ring. The structure of the reaction products was established by n.m.r., i.r., u.v. and mass spectroscopic methods. Electrophilic agents like protons, carboxylic acid chlorides or methyl iodide regenerate the original pyrylium cations from 7 . In refluxing methanol 7a is converted into the 2-methoxy-2H-pyran derivative 8 , whereas in aqueous acetone the pseudobase 9 and with ammonia the pyridine 10 are formed. Reaction of 7a with nitromethane or ethyl cyanoacetate provides the benzene derivatives 11 and 12 , respectively.     

Pyryliumverbindungen. 43 [1]. Arylsubstituierte 5-(2-Dialkylamino-thiazol-5-yl)-pentadienone aus 2,4,6-Triaryl-pyryliumsalzen und 2-Dialkylamino-4-arylthiazolen

Pyrylium Compounds. 43. Arylsubstituted 5-(2-Dialkylamino-thiazol-5-yl)-pentadienones from 2,4,6-Triarylpyrylium Salts and 2-Dialkylamino-4-aryl-thiazoles 2,4,6-Triarylpyrylium salts 1 react with 2-dialkylamino-4-aryl-thiazoles 7 (used in substance or prepared in situ from α-thiocyanato-acetophenones 9 ) in the presence of an appropriate acid-binding agent (e.g. piperidine acetate or sodium acetate) to give 5-(2-dialkylamino-4-aryl-thiazol-5-yl)-1,3,5-triaryl-penta-2,4-dien-1-ones 8 . As reaction medium aliphatic alcohols (ethanol, n-propanol), dipolar aprotic solvents (acetonitrile) or chlorinated hydrocarbons (methylene chloride, chloroform) can be used. On the other hand, under the same conditions 2-amino-4-phenyl-thiazole ( 10 ) reacts with salts of type 1 via pyrylium ring transformation yielding 2,4,6-triaryl-1-(4-phenyl-thiazol-2-yl)-pyridinium perchlorates 11 .     

Ringtransformationen heterocyclischer Verbindungen. I. 2-Amino-benzophenone und 7-Oxo-hepta-2,4-diennitrile durch Reaktion von 2,4,6-Triaryl-pyryliumsalzen mit 4-Nitro-benzylcyanid

Ring Transformations of Heterocyclic Compounds. I. 2-Amino-benzophenones and 7-Oxo-hepta-2,4-dienenitriles by Reaction of 2,4,6-Triarylpyrylium Salts with 4-Nitrobenzyl Cyanide 2,4,6-Triarylpyrylium salts 1 react with 4-nitrobenzyl cyanide in the presence of sodium acetate, triethylamine or triethylamine/acetic acid to give 7-oxo-hepta-2,4-dienenitriles 2 . With stronger bases such as sodium methanolate or ethanolate a ring transformation of the salts 1 occurs giving rise to 2-amino-benzophenones 3 which can also be obtained by cyclization of the nitriles 2 . Under the same conditions the 3-methyl-2,4,6-triphenylpyrylium salt 4 forms the 4-methyl-7-oxo-hepta-2,4-dienenitrile 5 by regioselective addition of the 4-nitrobenzyl cyanide at C-2 or it is converted to the 2-amino-5-methyl-benzophenone 6 . The ring transformation of the pyrylium salts 1 / 4 by 4-nitrobenzyl cyanide represents a new and simple method for the preparation of 2-amino-benzophenones. – Spectroscopic data of the novel compounds are discussed; the structure of 5 was confirmed by a single crystal X-ray analysis.     

Pyryliumverbindungen. XXVII. Spezifisch deuterierte Carbo- und Heterocyclen via 2,4,6-Triaryl-[3,5-2H2]pyryliumsalze

Pyrylium Compounds. XXVIII. Specifically Deuterated Carbo- and heterocycles via 2,4,6-Triaryl[3,5-²H₂]pyrylium Salts On heating with catalytic amounts of bases(e.g. triethyl amine) in deuterated alcohols such as methan[²H]ol or ethan[²H]ol pseudobases of 2, 4, 6-triarylpyrylium salts 1 undergo fast¹H/²H isotopic exchange reaction affording 1, 3, 5-triaryl[2, 4, 4-²H₃]pent-2-ene-1,5-diones which with [²H] perchloric acid give highly deuterated 2, 4, 6-triaryl-[3, 5-²H] pyrylium perchlorates 8 . These salts are obtainable also directly from 1 through a one-pot procedure by ring opening of the latter with deuterium oxide under the above-mentioned¹H/²H isotopic exchange conditions followed by recyclization of the formed 1, 3, 5-triaryl[2, 4, 4-²H₃]pent-2-ene-1, 5-diones with [²H]ClO₄. Ring transformations of 2, 4, 6-triphenyl[3, 5-²H²]pyrylium perchlorate (8a) to 2, 4, 6-triphenyl[3, 5-²H₂]nitrobenzene (9) 2, 4, 6-triphenyl[3, 5-²H₂]pyridine (10) , 1, 2, 4, 6-tetraphenyl[3, 5-²H₂]pyrydinium perchlorate (11) , 2, 4, 6-triphencyl[3, 5-²H₂]thiopyrylium perchlorate (12) , 2-benzoyl-3, 5-diphenyl[4-²H]furan (13) , and 3, 5, 7-triphenyl-[4, 4, 6-²H₃]4H-1, 2-diazepin (14) demonstrate the usability of pyrylium salts of type 8 as starting materials for syntheses of specifically deuterated carbo- and hetrocycles.     

Pyryliumverbindungen. 36. Substituierte Benzoesäureester aus 2,4,6-Triaryl-pyryliumsalzen und α-Ketocarbonsäureestern

Pyrylium Compounds. 36. Substituted Benzoic Acid Esters from 2,4,6-Triarylpyrylium Salts and α-Ketocarboxylic Acid Esters 2,4,6-Triarylpyrylium salts 1 react with α-ketocarboxylic acid esters 2 in the presence of two equivalents of an appropriate condensing agent (e.g. dialkylamine salts of weak acids, triethylamine/acetic acid, or sodium acetate) to give 2-aroyl-3,5-diarylbenzoic acid esters 3 . However, using only one equivalent of the condensing agent, the formation of 3,5-diarylbenzoic acid esters 5 predominates. Alkaline saponification of the new esters 3 and 5 yields the corresponding substituted benzoic acids 4 and 6 , respectively. – I.r., u.v., n.m.r. and mass spectroscopic data of the novel products 3 – 6 are reported.     

Pyryliumverbindungen. XXIX [1] Substituierte Benzophenone aus 2,4,6-Triaryl-pyryliumsalzen und Methyl(en)ketonen

Pyrylium Compounds. XXIX. Substituted Benzophenones from 2,4,6-Triarylpyrylium Salts and Methyl(ene) Ketones In the presence of piperidine acetate (or similar salts of certain dialkylamines), 2,4,6-triarylpyrylium perchlorates 5 react with methyl(ene) ketones 6 to give benzophenones 7 , the structure of which was proved by spectroscopic methods as well as by independent synthesis. Besides acetone and other acyclic ketones (e. g. alkyl methyl ketones, phenylacetone, desoxybenzoin, dibenzyl ketone) cyclic ketones (e. g. cyclopentanone, cyclohexanone, cycloheptanone, acenaphthenone) can also be used as ketone component 6 ; acetophenones react differently leading to hydrocarbons of the 1,3,5-triarylbenzene type 15 . The varying efficiency of the diverse amine salts and the mode of incorporation of the unsymmetrically substituted ketones suggest the intermediate formation of enamines 10 as crucial step of the ring transformations observed. This assumption is supported by isolation of the iminium salt 18 on reacting 3,5-dimethyl-2,4,6-triphenylpyrylium perchlorate ( 16 ) with acetone/piperidine acetate.     

Electrophilic Additions to Highly Reactive Enol Ethers. The Particular Role of Resonance in Determining the Kinetic Selectivity Evidenced by Extensive Comparison of Olefin Bromination and Hydration

The kinetic selectivity of aliphatic enol ethers, EtOCR = CHR' (R and R′ = H or Me), towards electrophiles, I₂, Br₂ and H₃O⁺, is expressed by the kinetic effect of a methyl substituent in the α position with respect to the ethoxy group, k_α-Me/k_H. As expected from the reactivity–selectivity principle, RSP, these selectivities are small, 16, 18 and 330, respectively, as compared to those observed for less reactive olefins. However, a more general comparison of the selectivities of various XCH = CH₂ olefins (X = Br, Me, Ph, OAc, OEt) reveals anomalies in their behavior with respect to the RSP: (i) enol ether iodination and bromination exhibit the same selectivity although their rates differ by 4 powers of ten, (ii) enol acetate and enol ether show similar selectivities in bromination but the rate of acetate is 3 × 10⁵ times smaller than that of ether and (iii) in hydration the selectivities of these two olefins are similar to that of styrene although rates range over 7 powers of ten from styrene to enol ether. In contrast with what was previously observed for homogeneous series of R-substituted styrenes (Ph(R)C = CH₂), there is no reactivity–selectivity relationship for electrophilic additions to XCH = CH₂ olefins. There is a parallelism, however, between the selectivities and the transition-state position estimated by the Brønsted exponents for hydration and by the Winstein–Grunwald coefficients for solvent effects on halogenations. These results are discussed in terms of different resonance effects on transition states and on reactivities which could arise from differences in the relative contributions of thermodynamic and intrinsic kinetic (Hammond effects) factors on the selectivities.     

Pyryliumverbindungen. XVIII, 2-Alkoxy-2H-pyrane aus tetra- und pentasubstituierten Pyryliumsalzen

Pyrylium Compounds. XVIII. 2-Alkoxy-2H-pyrans from Tetra- and Pentasubstituted Pyrylium Salts Alkali alkoxides add regioselectively to 2,3,4,6-tetrasubstituted pyrylium salts 7 (R' H), affording high yields of colourless crystalline 2-alkoxy-2H-pyrans 9 . The latte are also formed simply on refluxing 7 in the corresponding alcohol with triethylamine as proton acceptor. 3,5-Dialkylsubstituted 2,4,6-triarylpyrylium salts react analogously. The 2H-pyran structure of the adducts obtained follows from their n.m.r., i.r., u.v. and mass spectra as well as from their reaction with tetracyanoethylene to cycloadducts of type 10 . Acids regenerate from 9 the original pyrylium cations, whereas reaction of 9 with nitromethane or ethyl cyanoacetate provides benzene derivatives. -- The novel starting pyrylium salts 7b--o are characterized by u.v./vis data and by transformation into the corresponding pyridine derivatives     

硒催化CO/H2O体系下常压还原合成3-硝基-5-氨基-2,4,6-三甲基苯磺酸的研究

以硒为催化剂、CO为还原剂、水为氢源、无机弱碱为助催化剂、N,N-二甲基甲酰胺(DMF)作溶剂,常压下将3,5-二硝基-2,4,6-三甲基苯磺酸还原为3-硝基-5-氨基-2,4,6-三甲基苯磺酸。最优反应条件为:3,5-二硝基-2,4,6-三甲基苯磺酸1. 45 g (5 mmol),无水醋酸钠0. 492 g (6 mmol),DMF 30 m L,水3 m L,在95℃下回流反应5h。产物纯度可达87. 92%。     

Pyryliumverbindungen. 45 [1]. 4-Aroyl-fluorene aus 2,4,6-Triaryl-pyryliumsalzen und Indan-1-on via 2-(5-Oxo-pent-2-en-1-yliden)-indan-1-one

Pyrylium Compounds. 45. 4-Aroyl-fluorenes from 2,4,6-Triaryl-pyrylium Salts and Indan-1-one via 2-(5-Oxo-pent-2-en-1-yliden)-indan-1-ones 2,4,6-Triarylpyrylium salts 1 react with indan-1-one in the presence of an appropriate buffer system (e.g. piperidine acetate, triethylamine/acetic acid, triethylamine or sodium acetate) to yield the 2-(1,3,5-triaryl-5-oxo-pent-2-en-1-yliden)-indan-1-ones 2 . For the reaction medium aliphatic alcohols (methanol, ethanol), dipolar aprotic solvents (acetonitrile) or chlorinated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride) can be used. On treating 2 with sodium methanolate in methanol, a cyclization reaction occurs giving rise to the 4-aroyl-1,3-diaryl-fluorenes 3 . As by-products 1,3-diaryl-fluorenes 8 (e.g. 1,3-diphenyl-fluorene) are formed. - I.r., n.m.r. and u.v. spectroscopic data of the novel compounds 2 and 3 are reported.     

New organic polymers,II. Synthesis and characterization of poly[3,3′-(6,6′-bis-(2-substituted-4-quinazolonediyl)) alkylene]s

Poly[3,3′-(6,6′-bis-(2-substituted-4-quinazolonediyl))alkylene]s have been synthesized by reacting 6,6′-bis-(2-R-3,1,4-benzoxazinone) (R = Me, Ph, and ? CH₂Ph) with aliphatic diamines H₂N(CH₂)_nNH₂ with n = 0, 2, 3, 4, 6 and 8 in m-cresol. These polymers are insoluble in all common organic solvents but are fairly soluble in concentrated sulfuric acid. The polymers were characterized by IR spectral study, viscometric measurements and thermal analysis. IR spectra of the polymer samples have been compared with those of their model compounds.     

Primary steps of oxidation and electronic interactions in anodic cleavage of α,ω-diisocyanurate substituted dialkyl disulfides

The electrochemical oxidation of 1,1′-bis(3,5-dimethyl-[1,3,5]triazinane-2,4,6-trionyl)-α,α′-diorganyl-ω,ω′-disulfides involves a fast electron transfer followed by two chemical steps according to a ECC scheme. Using MM+, PM3 and ab initio SCF/3-21G^∗ molecular modeling it was shown that the low oxidation potential and the smallest current-determining cleavage rate constant in the reaction series of the disulfide with (CH₂)₆ spacer between SS bridge and the terminal heterocycles is due to an interaction of the π-components of the highest filled orbitals of the two heterocycles (HOMO and HOMO-1) with the LUMO (n-orbital of S) of the cation radical.     

The formation of [RuCl(p-cymene)(Me2HPz)(PPh2OR)]Cl (Me2HPz=3, 5-dimethylpyrazole; R=H,Me and p-Tol) complexes from the cleavage of the P–N bond of a P-coordinated P(Me2Pz)Ph2 ligand by ROH molecules in a ruthenium(II) complex. Crystal structure of [RuCl(p-cymene)(Me2HPz)(PPh2OH)]Cl

The complex [RuCl₂(p-cymene)]₂ reacts with 1-(3,5-dimethyl)pyrazolyldiphenylphosphine (P(Me₂Pz)Ph₂) to give the complex RuCl₂(p-cymene)(P(Me₂Pz)Ph₂). This compound reacts with ROH molecules (R=H, Me and p-Tol) to give [RuCl(p-cymene)(Me₂HPz)(PPh₂OR)]Cl (R=H, Me and p-Tol) complexes, which contain both Me₂HPz and PPh₂OR coordinated molecules.     

Novel [Ruthenium(substituted‐tetramethylcyclopentadiene) (2‐quinolinecarboxylato)(allyl)] Hexafluorophosphate Complexes as Efficient Catalysts for Highly Regioselective Nucleophilic Substitution of Aliphatic Allylic Substrates

Stable [ruthenium(R‐substituted‐tetramethylcyclopentadiene)(2‐quinolinecarboxylato)(1‐R′‐substituted‐allyl) hexafluorophosphate (R=Me, R′=H, Me, n‐Pr, Ph; R=t‐Bu, R′=Me) and [ruthenium(pentamethylcyclopentadiene)(2‐quinolinecarboxylato)(1‐n‐propylallyl)] tetrafluoroborate ( 4′a ), as allylruthenium(IV) complexes, have been synthesized in one step, starting from [ruthenium(R‐substituted‐tetramethylcyclopentadiene)tris(acetonitrile) hexafluorophosphate or tetrafluoroborate complexes, quinaldic acid, and allylic alcohols. Single stereoisomers are obtained and the X‐ray single crystal structure determinations of 3b (R=t‐Bu, R′=Me) and 4′a allow one to specify the preferred arrangement. Complexes 3a (R=R′=Me) and 3b are involved as precatalysts favoring the formation of branched products in regioselective nucleophilic allylic substitution reactions, starting from ethyl 2‐(E)‐hexen‐1‐yl carbonate and chlorohexene as unsymmetrical aliphatic allylic substrates. Phenols, dimethyl malonate, and primary (aniline) and secondary (pyrrolidine, piperidine) amines have been used as nucleophiles under mild basic conditions. For the first time, the regioselectivity in favor of the branched product obtained from purely aliphatic allylic substrates is close to the high regioselectivity previously reached starting from cinnamyl‐type substrates in the presence of ruthenium catalysts.