346587-69-7Relevant academic research and scientific papers
Rhodium-Catalyzed [2+2+2] Cycloaddition Reactions of Linear Allene–Ene–Ynes to afford Fused Tricyclic Scaffolds: Insights into the Mechanism
Cassú, Daniel,Parella, Teodor,Solà, Miquel,Pla-Quintana, Anna,Roglans, Anna
, p. 14889 - 14899 (2017/10/27)
Allene-(E)-ene-yne N-tosyl-tethered substrates 3 a–3 h were efficiently prepared and their rhodium-catalyzed [2+2+2] cycloaddition reactions were evaluated. The cycloadditions are chemoselective as only the proximal double bond of the allene reacted to af
Polyoxometalate-Gold(I)/H+ Complexes: Air-Stable, Efficient, Polyvalent, and Bifunctional Catalysts
Hueber, Damien,Hoffmann, Marie,De Frémont, Pierre,Pale, Patrick,Blanc, Aurélien
supporting information, p. 5065 - 5072 (2015/11/09)
Gold(I)/H+-polyoxometalate hybrids, with general formula [POM]x-[H]x-1+[R3PAu(MeCN)]+, were synthesized and fully characterized by 31P and 29Si MAS or liquid NMR, FT-I
Copper-catalyzed domino homologation and cycloisomerization reactions for 3-pyrroline synthesis
Shin, Ye Ho,Maheswara, Muchchintala,Hwang, Joon Young,Kang, Eun Joo
supporting information, p. 2305 - 2311 (2014/04/17)
Copper bromide was found to be an efficient catalyst for a domino reaction sequence leading to 3-pyrrolines. The Cu(I)-catalyzed Crabbe reaction of propargyl sulfonamide and selective cycloisomerization of the allene intermediate were carried out using microwave irradiation conditions affording a wide range of 2-substituted- and 2,5-disubstituted-3-pyrrolines. Mechanistic studies of the reaction intermediates revealed two possible reaction pathways; both invoke the importance of vinyl copper intermediates.
A highly regio- and stereoselective formation of bicyclo[4.2.0]oct-5-ene derivatives through thermal intramolecular [2 + 2] cycloaddition of allenes
Ohno, Hiroaki,Mizutani, Tsuyoshi,Kadoh, Yoichi,Aso, Akimasa,Miyamura, Kumiko,Fujii, Nobutaka,Tanaka, Tetsuaki
, p. 4378 - 4389 (2008/02/05)
(Chemical Equation Presented) Thermal [2 + 2] cycloaddition of allenes with an additional multiple bond is described. By simply heating the allenenes or allenynes having a three-atom tether in an appropriate solvent such as dioxane or DMF, the distal doub
Silylstannylation of allenes and silylstannylation-cyclization of allenynes. Synthesis of highly functionalized allylstannanes and carbocyclic and heterocyclic compounds
Kumareswaran, Ramaiah,Shin, Seunghoon,Gallou, Isabelle,RajanBabu
, p. 7157 - 7170 (2007/10/03)
Catalyzed by Pd(0), trialkylsilyltrialkylstannane (R3Si- SnR′3) reagents undergo highly selective additions to 1,2-dien-7-ynes and 1,2-dien-8-ynes to give 2-vinylalkylidenecyclopentanes with silicon and tin substituents on the double bonds. Similar additions of distannanes and borostannanes show that the reactions with silylstannanes are superior in terms of ease of handling of the bifunctional reagents and the isolation of the products after the reaction. The chemo- and regioselectivities are controlled by the enhanced reactivity of the allene unit, while the (Z)-geometry of the exocyclic stannylvinylidene is a consequence of the syn-carbometalation and subsequent reductive elimination from Pd with retention of configuration at the vinyl carbon. Synthesis of highly functionalized pyrrolidines and indolizidines and the reluctance of certain kinds of allenynes and silicon-tin reagents to undergo the cyclization illustrate the scope and limitations of the reaction. Based on the isolation of intermediates, a mechanism for the formation of the cyclic compounds is proposed. Model transition states to explain the stereoselectivity in cyclization of substituted allenynes are provided. Further elaboration using the vinyltin and vinylsilane moieties should lead to highly functionalized carbocyclic and heterocyclic compounds. Under similar conditions, addition of silylstannanes to highly functionalized allenes gives E-allylstannanes with high stereoselectivity. Functional groups such as THP- and silyl-ethers, lactones, β- and γ-lactams, α,β-unsaturated esters, olefins, and substituted acetylenes are tolerated under the reaction conditions.
Synthesis of allenes from allylic alcohol derivatives bearing a bromine atom using a palladium(0)/diethylzinc system
Ohno, Hiroaki,Miyamura, Kumiko,Tanaka, Tetsuaki,Oishi, Shinya,Toda, Ayako,Takemoto, Yoshiji,Fujii, Nobutaka,Ibuka, Toshiro
, p. 1359 - 1367 (2007/10/03)
A general and efficient synthesis of allenes using a palladium(0)/diethylzinc system is described. Treatment of mesylates or trichloroacetates of (E)- or (Z)-2-bromoalk-2-en-1-ols with diethylzinc in the presence of a catalytic amount of palladium(0) affords allenes bearing an aminoalkyl, alkyl, or aryl substituent(s) in good to high yields. No transfer of chirality from the stereogenic center carrying the mesyloxy group to the allene was observed.
