Synthesis and Application of Tetrafluoroethylene (CF2CF2)-Containing Acetylene Derivatives

Synthesis ◽  
2020 ◽  
Vol 52 (13) ◽  
pp. 1947-1958
Author(s):  
Tsutomu Konno ◽  
Gen Egashira ◽  
Chihiro Kajimoto ◽  
Takuto Kataoka ◽  
Shigeyuki Yamada
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Alder Reaction ◽  
Diels Alder ◽  
Benzene Derivatives ◽  
Diels Alder Reaction ◽  
Cross Coupling Reaction ◽  
Oxidative Aromatization ◽  
High Yields ◽  
Acetylene Derivatives

On treating 1,3,4-tribromo-1,1,2,2-tetrafluorobutane, readily prepared from commercially available 4-bromo-3,3,4,4-tetrafluorobut-1-ene, with 3.3 equivalents of LHMDS at 0 °C in THF, the corresponding lithium acetylide could be prepared quantitatively. The acetylide reacted well with various aldehydes, ketones, or chlorosilanes to give the corresponding acetylene derivatives in high yields. It was also found that various iodoarenes could participate in the cross-coupling reaction with the zinc acetylide, readily prepared from the lithium acetylide and ZnCl2·TMEDA complex, in the presence of Pd(PPh3)4 to bring about the adducts in high yields. Thus-obtained acetylene derivatives underwent smooth Diels–Alder reaction with various 1,3-dienes to afford the corresponding 1,4- or 1,3-cyclohexadiene derivatives. In addition, it was revealed that the oxidative aromatization of the resulting cyclohexadiene derivatives with DDQ took place very smoothly, providing the multi-substituted benzene derivatives having a tetrafluoro­ethylene group.

scholarly journals Synthesis of 3,4-dihydro-1,8-naphthyridin-2(1H)-ones via microwave-activated inverse electron-demand Diels–Alder reactions

2014 ◽  
Vol 10 ◽  
pp. 282-286 ◽  
Author(s):  
Salah Fadel ◽  
Youssef Hajbi ◽  
Mostafa Khouili ◽  
Said Lazar ◽  
Franck Suzenet ◽  
...  
Keyword(s):  
Coupling Reaction ◽  
Alder Reaction ◽  
Diels Alder ◽  
Aryl Halides ◽  
Side Chain ◽  
Terminal Alkyne ◽  
Inverse Electron Demand ◽  
Diels Alder Reaction ◽  
Cross Coupling Reaction ◽  
Electron Demand

Substituted 3,4-dihydro-1,8-naphthyridin-2(1H)-ones have been synthesized with the inverse electron-demand Diels–Alder reaction from 1,2,4-triazines bearing an acylamino group with a terminal alkyne side chain. Alkynes were first subjected to the Sonogashira cross-coupling reaction with aryl halides, the product of which then underwent an intramolecular inverse electron-demand Diels–Alder reaction to yield 5-aryl-3,4-dihydro-1,8-naphthyridin-2(1H)-ones by an efficient synthetic route.

Ferromagnetic Chain Based on Verdazyl-Nitroxide Diradical

2020 ◽  
Author(s):  
Evgeny Tretyakov ◽  
Svetlana Zhivetyeva ◽  
Pavel Petunin ◽  
Dmitry Gorbunov ◽  
Nina Gritsan ◽  
...  
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Ferromagnetic Coupling ◽  
Nitronyl Nitroxide ◽  
Triplet Ground State ◽  
One Dimensional ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed ◽  
Ferromagnetic Chain ◽  
High Yields

<p>Verdazyl-nitroxide diradicals were synthesized using the palladium-catalyzed cross-coupling reaction of the corresponding iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields (up to 82%). The synthesized diradicals were found to be highly thermally stable and have a singlet (D<i>E</i><sub>ST</sub> » -64 cm<sup>–1</sup>) or triplet ground state (D<i>E</i><sub>ST</sub> ³ 25 and 100 cm<sup>–1</sup>), depending on which canonical hydrocarbon diradical type they belong to. Upon crystallization, triplet diradicals form unique one-dimensional (1D) spin <i>S</i> = 1 chains of organic diradicals with intrachain ferromagnetic coupling of <i>J</i>′/<i>k</i><sub>B</sub> from 3 to 6 K.</p>

An Iron-Based Catalyst Enables The Enantioconvergent Synthesis of Chiral 1,1-Diarylalkanes Through a Suzuki-Miyaura Cross-Coupling Reaction

2020 ◽  
Author(s):  
Chet Tyrol ◽  
Nang Yone ◽  
Connor Gallin ◽  
Jeffery Byers
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Radical Intermediates ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Boronic Esters ◽  
Carbon Centered Radical ◽  
Iron Based ◽  
High Yields

By using an iron-based catalyst, access to enantioenriched 1,1-diarylakanes was enabled through an enantioselective Suzuki-Miyaura crosscoupling reaction. The combination of a chiral cyanobis(oxazoline) ligand framework and 1,3,5-trimethoxybenzene additive were essential to afford high yields and enantioselectivities in cross-coupling reactions between unactivated aryl boronic esters and a variety of benzylic chlorides, including challenging ortho-substituted benzylic chloride substrates. Mechanistic investigations implicate a stereoconvergent pathway involving carbon-centered radical intermediates.

Regiospecific Palladium-Catalyzed Cross-Coupling Reactions Using the Operational Equivalent of 1,3-Dilithiopropyne

Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2387-2394 ◽  
Author(s):  
Jorge A. Cabezas ◽  
Natasha Ferllini
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Terminal Alkyne ◽  
Copper Iodide ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed ◽  
High Yields

A regiospecific palladium-catalyzed cross-coupling reaction using the operational equivalent of the dianion 1,3-dilithiopropyne, with aromatic iodides is reported. This reaction gives high yields of 1-propyn-1-yl-benzenes and 2-(propyn-1-yl)thiophenes in the presence of catalytic amounts of palladium(0) or (II) and stoichiometric amounts of copper iodide. No terminal alkyne or allene isomers were detected. Reaction conditions were very mild and several functional groups were tolerated.

Copper(i)/TF-BiphamPhos catalyzed asymmetric nitroso Diels–Alder reaction

2017 ◽  
Vol 53 (10) ◽  
pp. 1657-1659 ◽  
Author(s):  
Jun Li ◽  
Hai-Yan Tao ◽  
Chun-Jiang Wang
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Highly Efficient ◽  
Diels Alder Reaction ◽  
Cyclic Dienes ◽  
High Yields

A highly efficient enantioselective nitroso Diels–Alder reaction of 6-methyl-2-nitroso pyridine with various 1,3-dienes was successfully developed using a copper(i)/(S)–TF-BiphamPhos complex as the catalyst. For most of the cyclic dienes, the cycloadducts were obtained in high yields with excellent regio-, and stereoselectivities. Acyclic 2-silyloxy-1,3-diene also worked well in the reaction.

Sign in / Sign up

Export Citation Format

Share Document