Nucleophilic addition to acetylenes in superbasic catalytic systems. 12. Vinylation of lupinine

The addition of a natural alkaloid lupinine to acetylene in the presence of superbasic catalytic systems (KOH—DMSO, KOBu^t—DMSO, KOH—dioxane) under elevated or atmospheric pressure affords O-vinyllupinine (in up to 88% yield), a promising optically active monomer and intermediate for the preparation of new quinolizidine alkaloids. The same vinyl ether was obtained (in 60% yield) by the reaction of lupinine with vinyl acetate in the presence of Hg(OAc)₂.     

Nucleophilic addition to acetylenes in superbasic catalytic systems: XV. Vinylation of 2-hydroxymethylfuran

2-Hydroxymethylfuran reacted with acetylene in superbasic catalytic systems MOH-DMSO (M = Na, K) under mild temperature conditions (75–85°C, 1–2 h), yielding 80% of 2-vinyloxymethylfuran. The product, as well as acetaldehyde acetals derived therefrom, turned out to be promising as modifiers for electrolyte in lithium-sulfur rechargeable batteries.     

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVI. Vinylation of alcohols of the furan series under atmospheric pressure

2-Hydroxymethylfuran and 2-hydroxymethyltetrahydrofuran reacted with acetylene in the superbasic catalytic system KOH-DMSO at 75-85°C under atmospheric pressure to give in 1.5–3 h the corresponding 2-vinyloxymethyl derivatives in 88 and 91% yield, respectively.     

Nucleophilic addition of methanol and methanethiol to acetylene in the superbasic system KOH-DMSO: a quantum chemical model

Cluster-continuum models (KOH·nDMSO, n = 1, 5) were used to model the superbasic system “alkali metal hydroxide-dimethyl sulfoxide” within the framework of MP2/6-311++G**/ and B3LYP/6-31G* methods. The KOH molecule surrounded by five DMSO molecules exists as “solvate-loosened” ion pair with elongated K-O distance. It is proposed to consider the “solvate-loosened” ion pair of potassium cation with hydroxide anion in the surroundings of five solvent molecules as the catalytic coordination sphere of the superbasic system KOH-DMSO. Methanol and methanethiol molecules can be incorporated with ease into the first coordination sphere of potassium cation to form methoxide and methanethiolate ions. The possibility of nucleophilic attack of methoxide and methanethiolate ions on acetylene molecule in the first coordination sphere of potassium cation was studied. The model reaction system C₂H₂-CH₃OK-H₂O with one DMSO molecule included explicitly to maintain the “solvate-loosened” [CH₃O]^?...K⁺ ion pair and additional inclusion of solvent effects within the framework of the IEFPCM continuum model is the most preferable for serial calculations.     

Nucleophilic addition to iminium ethers in the preparation of functionalized N-alkyl heterocycles

Bicyclic iminium ethers can be synthesized by the reactions of ketones with hydroxyalkyl azides. These cationic species react with a variety of nucleophiles via two possible pathways. The initially formed, kinetic product arises from direct addition to the iminium carbon in the substrate. In some cases, the initial adduct reverts to the starting iminium ether and the ultimate product arises from nucleophilic displacement at the O-alkyl group to afford the terminally functionalized N-substituted amide. The behavior of a range of nucleophiles was studied by using several iminium ethers. In general, the relevant pathway could be identified by characterization of the product formed. For hydroxide addition, which can afford only one product regardless of mechanism, the reaction was shown to arise by the kinetic pathway, using (18)O-labeled hydroxide. A one-pot synthesis of functionalized lactams entailing treatment of ketones first with hydroxyalkyl azides followed by nucleophilic addition was also developed.     

A new electrophilic addition to acetylenes. Synthesis of 1,2-iodofunctionalized olefins

Acetylenes react with bis(pyridine)iodo(I) tetrafluoroborate (1) in the presence of a wide variety of nucleophiles (F, Cl, Br, I, SCN, pyridine, OAc, anisole, H) to give 1,2-iodofunctionalized olefins (4).     

Nucleophilic Vinyl Substitution in the Synthesis of Heterocycles. (Review)

Published data on the synthesis of various heterocyclic compounds by the reaction of nucleophiles with electrophilic olefins containing a nucleophilic group are reviewed and analyzed.     

Nucleophilic Substitution of 4-Bromo-5-nitrophthalodinitrile: XVII. Synthesis and Properties of Bifunctionally Substituted Metal Phthalocyanines with Aryloxy and Nitro Groups

By substitution of bromine in 4-bromo-5-nitrophthalonitrile 4-(aryloxy)-5-nitrophthalonitriles were synthesized and, on their basis, cobalt and copper tetra(4-aryloxy-5-nitro)phthalo-cyanines were prepared. Spectral properties of the obtained octasubstituted phthalocyanines were investigated.     

Synthesis and structure of some ruthenium-rhenium heterodinuclear complexes and their catalytic activity in the addition of carboxylic acids to phenylacetylene

The salt elimination reaction of Na[Re(CO)₅] with Cp*Ru(dppm)Cl, CpRu(dppm)Cl or CpRu(CO)₂Cl afforded the heterodinuclear species Cp*Ru(μ-CO)₂(μ-dppm)Re(CO)₃, Cp(CO)Ru(μ-dppm)Re(CO)₄, or Cp(CO)₂RuRe(CO)₅, respectively, in moderate yields. An orthometallated species, Cp*(CO)Ru(μ-H)[μ-PhP(C₆H₄)CH₂PPh₂]Re(CO)₃, was also obtained from the first reaction. All these heterodinuclear products have been characterised crystallographically. They also showed good catalytic activity for the addition of carboxylic acids to phenylacetylene to afford the anti-Markovnikov products selectively.     

Synthesis and polymerization reactions of cyclic imino ethers. VI. Polymers with biphenyl structure

A monomer of the AB‐type and a bifunctional comonomer of the AA‐type containing two 2‐oxazoline rings and a biphenyl structural unit were prepared from the corresponding carboxylic acids via their esterification and subsequent amidation with an aminoalcohol. The cyclization of an amide to 2‐oxazoline structure was achieved by treatment with thionyl chloride followed by liberation of the free base with sodium hydrocarbonate in an aqueous solution. The prepared monomers were used for the polyaddition polymerization of the AB‐type monomer having a 2‐oxazoline and phenol group bound on adjacent rings of the biphenyl structure in solution. The monomer of the AA‐type was used for AA+BB‐type polyaddition reactions with aliphatic dicarboxylic acids. Both types of polymerizations have been performed in melt and in solution. The structures of the polymers were determined, and the thermal properties of the polymers were evaluated. Liquid‐crystalline (LC) structures of the prepared polymers were observed by DSC measurements and optical microscopy. The polyaddition reactions of the monomers containing a 2‐oxazoline ring and a biphenyl unit represent a new efficient way for the preparation of a biphenyl unit containing poly(ether amide)s and poly(ester amide)s. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Intramolecular carbenoid addition to 1,3-dienes. Synthesis of cyclopentene annulated ring systems.

Diazoketones containing a 1,3-diene moiety were decomposed to yield corresponding vinylcyclopropanes stereospecifically. Transformation of vinylcyclopropanes to cyclopentenes is described and the scope of the reaction is discussed.     

Acyl Iodides in Organic Synthesis: VI. Reactions with Vinyl Ethers

Reactions of acetyl iodide with butyl vinyl ether, 1,2-divinyloxyethane, phenyl vinyl ether, 1,4-di-vinyloxybenzene, and divinyl ether were studied. Vinyl ethers derived from aliphatic alcohols (butyl vinyl ether and 1,2-divinyloxyethane) react with acetyl iodide in a way similar to ethyl vinyl ether, i.e., with cleavage of both O–Csp2 and Alk–O ether bonds. From butyl vinyl ether, a mixture of vinyl iodide, butyl acetate, vinyl acetate, and butyl iodide is formed, while 1,2-divinyloxyethane gives rise to vinyl iodide, vinyl acetate, and 2-iodoethyl acetate. The reaction of acetyl iodide with divinyl ether involves cleavage of only one O–Csp2 bond, yielding vinyl acetate and vinyl iodide. In the reactions of acetyl iodide with phenyl vinyl ether and 1,4-divinyloxybenzene, only the O–CVin bond is cleaved, whereas the O–CAr bond remains intact.     

The addition of methylborylene to acetylenes: Synthesis of 1,4-diboracyclohexa-2,5-dienes,and of a borirene and a diboretene derivative

The synthesis of 1,4-dimethyl-2,3,5,6-tetra-n-alkyl-1,4-diboracyclohexa-2,5-dienes from the reaction of di-n-alkylacetylenes with the methylborylene-generating system 2C₈K/MeBBr₂ is described. A mechanism for these reactions is proposed. The addition of methylborylene to di-t-butylacetylene results in the formation of 1-methyl-2,3-di-t-butylborirene and of 1,3-dimethyl-2,4-di-t-butyl-1,3-diboretene.