Methods of Preparation and Properties of Substituted Vinyl Ethers and Sulphides

Shostakovskii, M. F.; Gracheva, E. P.; Kul'bovskaya, N K

doi:10.1070/rc1961v030n04abeh002966

Cited by 15 publications

(5 citation statements)

References 2 publications

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“…The transannular addition of 4-chlorophenol to 1,1′-dialkynylferrocene was reported recently . The reactivity of internal unactivated alkynes with oxygen-bearing nucleophiles is poor compared to that of terminal alkynes. , Considering the above shortcomings, we envisioned that the simple intermolecular addition of phenols to unactivated alkynes is a challenging problem (eq ) . It would provide a novel synthetic strategy for creating a range of arylvinyl ether skeletons exclusively with Z -olefin stereochemistry in one step.…”

Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Intermolecular Hydrophenoxylation of Unactivated Internal Alkynes

2010

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A general and simple strategy for the synthesis of functionally diverse arylvinyl ethers is reported through gold-catalyzed intermolecular addition of electronically and sterically substituted phenols with unactivated alkynes. Addition of phenols to unsymmetrical alkynes provides the corresponding mixture of regioisomers with appreciable selectivity. Multiple hydrophenoxylations of polyphenols with diphenylacetylene are demonstrated successfully.

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Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Intermolecular Hydrophenoxylation of Unactivated Internal Alkynes

2010

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“…The branched product A can be obtained by Michael addition when the alkyne isomerizes to an allene or internal alkyne; these procedures are consequently limited to certain aliphatic alkynes. Other methods to prepare isomer A involve the use of Hg salts or elevated reaction temperatures (>120 °C), which often results in poor regioselectivity . Overall, synthetic approaches to branched alkyl vinyl sulfides ( A , R = alkyl), which have significant potential for use in synthesis, are very limited.…”

mentioning

confidence: 99%

“…Other methods to prepare isomer A involve the use of Hg salts or elevated reaction temperatures (>120 °C), which often results in poor regioselectivity. 12 Overall, synthetic approaches to branched alkyl vinyl sulfides (A, R ) alkyl), which have significant potential for use in synthesis, are very limited.…”

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confidence: 99%

Rhodium-Catalyzed Alkyne Hydrothiolation with Aromatic and Aliphatic Thiols

2005

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Alkyne hydrothiolation is a potentially attractive method for the formation of vinyl sulfides, which are valuable synthetic intermediates. Known methods for hydrothiolation using alkyl thiols are quite limited. We report herein that Tp*Rh(PPh3)2 (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) is a highly active catalyst for alkyne hydrothiolation with alkyl and aryl thiols. Hydrothiolation using alkyl thiols proceeds with excellent regioselectivity, providing convenient access to branched alkyl vinyl sulfides, which are difficult to synthesize by other means. A mixture of regioisomers is obtained when using aryl thiols, with the branched isomer as the major product, opposite that reported for other Rh complexes.

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“…In fact, the alkyl substituent on the double bond of an enol ether greatly affects its polymerizability and behavior even in cationic homopolymerization. For example, the living cationic polymerization of α‐methyl VEs or β‐methyl VEs was achieved only at temperatures much lower than those for VEs due to frequent side reactions . Cyclic enol ethers, β‐substituted VE analogues, have distinct polymerization reactivities compared with their acyclic counterparts.…”

Section: Introductionmentioning

confidence: 99%

“…For example, the living cationic polymerization of a-methyl VEs or b-methyl VEs was achieved only at temperatures much lower than those for VEs due to frequent side reactions. [6][7][8][9][10][11][12][13][14][15][16] Cyclic enol ethers, b-substituted VE analogues, have distinct polymerization reactivities compared with their acyclic counterparts. Such uniqueness in polymerizability is partially attributable to the ring strain of the monomers in addition to their steric hindrance.…”

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confidence: 99%

Controlled cationic alternating copolymerization of various enol ethers and benzaldehyde derivatives: Effects of enol ether structures

Ishido

Kanazawa

Kanaoka

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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Significant structural effects of enol ether monomers were demonstrated in cationic alternating copolymerizations with benzaldehyde derivatives (BzAs). a-Methyl, b-methyl, b,b-dimethyl, and cyclic enol ethers were copolymerized with BzAs by the EtSO 3 H/GaCl 3 system with 1,4-dioxane in toluene at 278 C. b-Methyl and cyclic monomers, b-monosubstituted compounds, induced copolymerizations with BzAs, some of which were well controlled to yield alternating copolymers with controlled molecular weights (MWs) and narrow MW distributions. Conversely, an a-methyl vinyl ether (VE) did not copolymerize with BzAs at all, probably due to its high reactivity and unfavorable ketal linkage formations. In addition, a b,b-dimethyl VE underwent only cyclotrimerizations because of its larger steric repulsion. The product alternating copolymers, especially those with cyclic units, exhibited improved thermal properties compared to those with simple VEs units. Under appropriate conditions, the alternating copolymers selectively degraded into the corresponding cinnamaldehyde derivatives by acid hydrolysis.

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Methods of Preparation and Properties of Substituted Vinyl Ethers and Sulphides

Cited by 15 publications

References 2 publications

Gold-Catalyzed Intermolecular Hydrophenoxylation of Unactivated Internal Alkynes

Gold-Catalyzed Intermolecular Hydrophenoxylation of Unactivated Internal Alkynes

Rhodium-Catalyzed Alkyne Hydrothiolation with Aromatic and Aliphatic Thiols

Controlled cationic alternating copolymerization of various enol ethers and benzaldehyde derivatives: Effects of enol ether structures

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