Vinylindenes and some heteroanalogues in the Diels-Alder reaction. III. Benzoquinone, 1,4-Naphthoquinone and Benzo[b]thiophen 1,1-Dioxide as dienophiles

1977 ◽  
Vol 30 (7) ◽  
pp. 1523 ◽  
Author(s):  
R Bergamasco ◽  
QN Porter
Keyword(s):  
Mass Spectrometry ◽  
Alder Reaction ◽  
Diels Alder ◽  
Skeletal Rearrangement ◽  
Diels Alder Reaction ◽  
High Yields

3-Vinylindene gives high yields of adducts with 1,4-benzoquinone, 1,4- naphthoquinone, and benzo[b]-thiophen 1,1-dioxide. The structures and stereochemistries of the adducts are confirmed by p.m.r. and mass spectrometry. The effects of various oxidation procedures on the 1,4- naphthoquinone adduct are described; no skeletal rearrangement accompanies oxidation with oxygen in base. Some adducts of 34sopropenylindene and 2-methyl-3-vinylindene are also described.

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.

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.

Vinylindenes and some heteroanalogues in the Diels-Alder reaction. II. Substituted fluorenes from 3-vinylindenes

1977 ◽  
Vol 30 (5) ◽  
pp. 1061 ◽  
Author(s):  
R Bergamasco ◽  
QN Porter
Keyword(s):  
Mass Spectrometry ◽  
Maleic Anhydride ◽  
Alder Reaction ◽  
Diels Alder ◽  
Dimethyl Acetylenedicarboxylate ◽  
Diels Alder Reaction

3-Vinylindene, 2-methyl-3-vinylindene and 3-isopropenylindene give normal, photostable adducts with ethenetetracarbonitrile by a Diels- Alder process. The first diene gives adducts with maleic anhydride, N- phenylmaleimide and dimethyl acetylenedicarboxylate. Where there is stereochemical ambiguity the adducts are shown by mass spectrometry to be exclusively endo. Two heterocyclic analogues are formed from 3- vinylindene with p-toluenesulphonyl cyanide and N-sulphinyl-p- toluenesulphonamide.

scholarly journals Synthesis of dibenzosuberenone-based novel polycyclic π-conjugated dihydropyridazines, pyridazines and pyrroles

2021 ◽  
Vol 17 ◽  
pp. 719-729
Author(s):  
Ramazan Koçak ◽  
Arif Daştan
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Cycloaddition Reactions ◽  
Inverse Electron Demand ◽  
Diels Alder Reaction ◽  
Reductive Treatment ◽  
High Yields ◽  
Derivatives Of ◽  
Electron Demand

The synthesis of novel polycyclic π-conjugated dihydropyridazines, pyridazines, and pyrroles was studied. Dihydropyridazine dyes were synthesized by inverse electron-demand Diels–Alder cycloaddition reactions between a dibenzosuberenone and tetrazines that bear various substituents. The pyridazines were synthesized in high yields by oxidation of dihydropyridazine-appended dibenzosuberenones with PIFA or NO. p-Quinone derivatives of pyridazines were also obtained by H-shift isomerization following the inverse electron-demand Diels–Alder reaction of tetrazines with p-quinone dibenzosuberenone. Then these pyridazines were converted to the corresponding pyrroles by reductive treatment with zinc. It was observed that all the dihydropyridazines obtained gave absorbance and emission at long wavelengths.

Multiple Activation Catalyst for Asymmetric [4+2] Cycloaddition of Aldehydes with Dienes

Synlett ◽  
2021 ◽  
Author(s):  
Takuya Kurahashi ◽  
Seijiro Matsubara ◽  
Rei Tomifuji ◽  
Shunpei Murano ◽  
Satoru Teranishi ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Addition Reaction ◽  
Catalyst System ◽  
Alder Reaction ◽  
Diels Alder ◽  
Functional Theory ◽  
Diels Alder Reaction ◽  
Chiral Phosphoric Acid ◽  
High Yields

AbstractThe enantioselective oxa-Diels–Alder reaction of nonactivated substrates by utilizing FeCl3 and a 1,1′-bi-2-naphthol (BINOL) derived chiral phosphoric acid as a multiple activation catalyst is reported. Various oxygen-containing six-membered heterocycles were obtained in high yields and in an enantioselective manner. Density functional theory (DFT) calculations elucidate that both Lewis acidic and Brønsted acidic moieties in the catalyst system synergistically activate two lone pairs of an aldehyde to facilitate enantioselective addition reaction of dienes.

Four-step one-pot catalytic asymmetric synthesis of multisubstituted tricyclic compounds: Lipase-catalyzed dynamic kinetic resolution followed by an intramolecular Diels–Alder reaction

Synlett ◽  
2021 ◽  
Author(s):  
Izuru Tsuchimochi ◽  
Shuhei Hori ◽  
Yasuo Takeuchi ◽  
Masahiro Egi ◽  
Tomo-o Satoh ◽  
...  
Keyword(s):  
Hydroxy Group ◽  
Kinetic Resolution ◽  
Alder Reaction ◽  
Diels Alder ◽  
One Pot ◽  
Diels Alder Reaction ◽  
Tricyclic Compounds ◽  
High Yields ◽  
Group Migration ◽  
Oxovanadium Compounds

Starting from readily available tertiary alcohols, four different reactions (i.e., a 1,3-migration of a hydroxy group, kinetic resolution, racemization, and an intramolecular Diels–Alder reaction) took place under the co-catalysis of lipase and oxovanadium compounds in a one-pot process to produce multisubstituted tricyclic carbon frameworks in high yields and high enantioselectivities. The key to the success of this process was the discovery that the silyl group attached to the terminal carbon of the vinyl moiety completely controls the direction of hydroxy group migration.

scholarly journals Synthesis of Illisimonin a Skeleton by Intramolecular Diels–Alder Reaction of Ortho-Benzoquinones and Biomimetic Skeletal Rearrangement of Allo-Cedranes

Organics ◽  
2021 ◽  
Vol 2 (3) ◽  
pp. 306-312
Author(s):  
Takahiro Suzuki ◽  
Riko Nagahama ◽  
Muhammad Aiman Fariz ◽  
Yuki Yukutake ◽  
Kazutada Ikeuchi ◽  
...  
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Skeletal Rearrangement ◽  
Diels Alder Reaction

Illisimonin A is a new sesquiterpene isolated from Illicium simonsii, and it possesses a novel 5/5/5/5/5 pentacyclic skeleton. The tricyclic skeleton of illisimonin A, tricyclo[5.2.1.01,5]decane, is presumed to be biosynthesized from allo-cedranes via a skeletal rearrangement. Herein, we report the concise synthesis of highly oxidized allo-cedranes by an intramolecular Diels–Alder reaction using ortho-benzoquinones and demonstrate the biomimetic transformation of allo-cedranes by a retro-Claisen/aldol pathway.

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