Efficient Catalytic Insertion of Acetylenes into a Carbon−Carbon Single Bond of Nonstrained Cyclic Compounds under Mild Conditions

Kuninobu, Yoichiro; Kawata, and Atsushi; Takai, Kazuhiko

doi:10.1021/ja064022i

Cited by 103 publications

(42 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Instead of producing the same adduct, we obtained an eight-membered ring product, 24, quantitatively (eq. 11) [7]. The structure of the eight-membered carbocycle was confirmed by X-ray crystallographic analysis of the corresponding thioacetal of 24.…”

Section: Insertion Of Alkynes Into a Nonstrained C-c Single Bond Of ␤mentioning

confidence: 90%

Rhenium- and manganese-catalyzed carbon–carbon bond formation using 1,3-dicarbonyl compounds and alkynes

Kuninobu

Kawata

et al. 2010

Pure and Applied Chemistry

Self Cite

View full text Add to dashboard Cite

A rhenium complex, [ReBr(CO) 3 (thf)] 2 , catalyzed insertion of terminal alkynes into a C-H bond of active methylene sites of 1,3-dicarbonyl compounds. When a catalytic amount of isocyanide or molecular sieves was added to the reaction mixture, the reaction course changed markedly, and insertion of alkynes into a C-C single bond between αand β-positions of cyclic and acyclic β-keto esters occurred. The formed acyclic δ-keto esters could be converted to 2-pyranones, which were applied to the synthesis of multisubstituted aromatic compounds via the Diels-Alder reaction and successive elimination of carbon dioxide. In the case of the rhenium-catalyzed reactions between terminal alkynes and β-keto esters without substituent at the α-position, tetrasubstituted benzenes were produced regioselectively by two-to-one reaction of the components. The yields of tetrasubstituted benzenes were improved by using a manganese catalyst.Scheme 5 Proposed mechanism for the synthesis of tetrasubstituted benzenes. Scheme 6Proposed mechanism for the synthesis of 2-pyranones.

show abstract

Section: Insertion Of Alkynes Into a Nonstrained C-c Single Bond Of ␤mentioning

confidence: 90%

Rhenium- and manganese-catalyzed carbon–carbon bond formation using 1,3-dicarbonyl compounds and alkynes

Kuninobu

Kawata

et al. 2010

Pure and Applied Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…42 It is usually difficult to construct medium size cyclic skeletons. By using this method, eight-, nine-, and ten-membered cyclic compounds can be synthesized from the corresponding six-, seven-, and eight-membered cyclic ¢-keto esters by a simple operation.…”

Section: 41mentioning

confidence: 99%

“…As a result, bicyclo[3.3.1]nonene derivatives were formed in excellent yields at lower temperature (Scheme 31). 44 A proposed reaction mechanism for the formation of bicyclo[3.3.1]nonene derivatives from the corresponding eight-membered cyclic compounds 42 is as follows: (1) isomerization of the olefin moiety from the keto to the enol form, and (2) intramolecular Claisen-type condensation via the elimination of ethanol.…”

Section: 41mentioning

confidence: 99%

Development of Novel and Highly Efficient Methods to Construct Carbon–Carbon Bonds Using Group 7 Transition-Metal Catalysts

Kuninobu

Takai

2012

Bulletin of the Chemical Society of Japan

Self Cite

View full text Add to dashboard Cite

Rhenium-or manganese-catalyzed transformations based on the cleavage of inactive bonds, such as carbon hydrogen and carboncarbon bonds are discussed. Such transformations are recognized as key methods to realize efficient and powerful reactions. We also reveal novel regio-and/or stereodefined cycloaddition reactions using a rhenium or manganese catalyst. Most of the catalytic activities are typical of rhenium and manganese carbonyl complexes.

show abstract

“…92 6-(2-Benzofuryl)purines are readily available via a one-pot Sonogashira coupling-cyclization between 6iodopurine and 2-ethynylphenol. Rearrangement to (119) and the formal 4 + 2-cycloaddition product (118) leads to the aromatized final (116), liberating the active catalyst. Acid-catalysed isomerization of the E-compound afforded the Z-isomer.…”

Section: Rearrangement Involving Organometallic Compoundsmentioning

confidence: 99%

Molecular Rearrangements: Part 2. Other Reactions

Brandi

Gensini

2010

Organic Reaction Mechanisms · 2006

View full text Add to dashboard Cite

The formation of α-phenyl-β-halovinyl cation, β-phenyl-α-halovinyl cation, and also the halogen-bridged and the spirocyclic phenyl-bridged cations, as intermediates of protonation of phenylethynyl halides, or of halogen addition to phenylethynes, has been evaluated by DFT at the B3LYP/6-31+G(d) level and, for comparison in representative cases, by B3LYP/6-311++G(d,p). 1 Structural and mechanistic studies of the lithium diisopropylamide (LDA)-mediated anionic Fries rearrangements of aryl carbamates have been described. 2 Substituents at the meta position of the arene (H, OMe, F) and the dialkylamino moiety of the carbamate (Me 2 N, Et 2 N, and i-Pr 2 N) markedly influence the relative rates of ortholithiation and subsequent Fries rearrangement. The mechanism of the Fries rearrangement of aryl formates promoted by boron trichloride has been studied by means of 1 H, 2 H, and 11 B NMR spectroscopy and DFT calculations. 3 After the formation of a 1:1 substrate -Lewis acid adduct, the rearrangement proceeds in two steps, beginning with the cleavage of the ester bond and the release of formyl chloride in situ, which, in turn, acts as a formylating agent, introducing 451

show abstract

Efficient Catalytic Insertion of Acetylenes into a Carbon−Carbon Single Bond of Nonstrained Cyclic Compounds under Mild Conditions

Cited by 103 publications

References 25 publications

Rhenium- and manganese-catalyzed carbon–carbon bond formation using 1,3-dicarbonyl compounds and alkynes

Rhenium- and manganese-catalyzed carbon–carbon bond formation using 1,3-dicarbonyl compounds and alkynes

Development of Novel and Highly Efficient Methods to Construct Carbon–Carbon Bonds Using Group 7 Transition-Metal Catalysts

Molecular Rearrangements: Part 2. Other Reactions

Contact Info

Product

Resources

About