1226977-80-5

Upstream product

• 536-74-3 phenylacetylene 
• 102684-91-3 2-bromo-5-(trifluoromethyl)benzaldehyde 

Downstream Products

• 1226977-94-1 10-phenyl-14-(trifluoromethyl)-15bH-isoquino[2,1-a]pyrrolo[2,1-c]quinoxaline 

Relevant academic research and scientific papers

Palladium-catalyzed cascade decarboxylative amination/6- endo-dig benzannulation of o-alkynylarylketones with n-hydroxyamides to access diverse 1-naphthylamine derivatives

An efficient and practical one-pot strategy to produce highly substituted 1-naphthylamines via sequential palladium-catalyzed decarboxylative amination/intramolecular 6-endo-dig benzannulation reactions has been described. In this reaction, a broad range of electron-rich, electron-neutral, and electron-deficient o-alkynylarylketones react well with N-hydroxyl aryl/alkylamides to give a diversity of 1-naphthylamines in good to excellent yields under mild reaction conditions. The gram-scale synthesis, with benefits such as undiminished product yield and easy transformation, illustrated the practicality of this method.

Tunable Synthesis of Indeno[1,2- c]furans and 3-Benzoylindenones via FeCl3-Catalyzed Carbene/Alkyne Metathesis Reaction of o-Alkynylbenzoyl Diazoacetates

An efficient synthesis of indeno[1,2-c]furan and 3-benzoylindenone derivatives through a FeCl3-catalyzed carbene/alkyne metathesis reaction of o-alkynylbenzoyl diazoacetates is presented. Mechanistically, the key intermediate, vinyl iron carbene, is formed by 5-exo-dig carbocyclization and terminated with a formal [3 + 2] cycloaddition or carbonylation. To the best of our knowledge, this is the first example in which FeCl3 is used as a catalyst for a carbene/alkyne metathesis reaction. Finally, derivatization reactions were carried out to showcase the value of the products.

Modular synthesis of 3-substituted isocoumarinsviasilver-catalyzed aerobic oxidation/6-endoheterocyclization ofortho-alkynylbenzaldehydes

A method involving silver-catalyzed aerobic oxidation/6-endoheterocyclization ofortho-alkynylbenzaldehydes to yield 3-substituted isocoumarins is described. The developed protocol allows convenient access to a range of synthetically useful 3-substituted isocoumarins and related fused heterocyclolactones in good to high yields, using silver tetrafluoroborate as the catalyst, and atmospheric oxygen as the terminal oxidant and the source of endocyclic oxygen. Mechanistic studies suggest the involvement of a free-radical pathway.

Polarization Effect on Regioselectivity of Pd-Catalyzed Cyclization of 2-Alkynylbenzaldehydes

We report a study on the relationship between the polarization of C≡C bond in a series of 2-alkynylbenzaldehydes and the regioselectivity of their Pd-catalyzed annulation reactions. The electrophilic and nucleophilic character of the triple bond carbon atoms was examined using 13C and HMBC NMR experiments. The direction of polarization is determined only by the formyl group and its position on an aromatic ring. On the other hand, the strength of the polarization expressed through chemical shift difference Δδ of acetylenic carbon atoms is a result of electron-withdrawing or electron-donating ability of the other substituent. Out of two possible regioisomers, the Pd-catalyzed cyclization reactions of 2-alkynylbenzaldehydes that were studied predominantly afforded 1H-isochromenes suggesting that the polarization of a triple bond is one of the contributing factors in the regioselectivity of this process.

A gold(i)-catalyzed intramolecular tandem cyclization reaction of alkylidenecyclopropane-containing alkynes

A novel gold(i)-catalyzed intramolecular tandem cyclization reaction of ortho-(arylethynyl)arenemethylenecyclopropanes provided an efficient approach to prepare functionalized 11H-benzo[a]fluorene derivatives in moderate to good yields. Further transformations as well as applications of the products have been presented and a plausible reaction mechanism has also been proposed on the basis of deuterium labeling and control experiments.

Highly selective construction of medium-sized lactams by palladium-catalyzed intramolecular hydroaminocarbonylation of aminoalkynes

A novel palladium-catalyzed intramolecular hydroaminocarbonylation of aminoalkynes has been developed. This direct and operationally simple protocol provides a rapid and reliable approach to a diverse array of valuable seven-and eight-membered lactams with high chemoselectivity and regioselectivity. The high selectivity might be attributed to rational tuning the electronic nature of the amine moiety and the palladium catalyst which enabled this transformation to proceed in the absence of acidic or any other additives under fairly mild reaction conditions. This method paves the way for the synthesis of medium-sized lactams.

Metal/Benzoyl Peroxide (BPO)-Controlled Chemoselective Cycloisomerization of (o-Alkynyl)phenyl Enaminones: Synthesis of α-Naphthylamines and Indeno[1,2-c]pyrrolones

Synthetic methods involving chemoselective tandem reactions for the synthesis of α-naphthylamines and indeno[1,2-c]pyrrolones starting from (o-aklynyl)phenyl enaminones are described. When reactions were carried out in N,N-dimethylformamide (DMF) using a AgNO3 catalyst, α-naphthylamines were obtained in up to 89% isolated yields within 2 h. Whereas indeno[1,2-c]pyrrolones were produced in high isolated yields in the presence of benzoyl peroxide (BPO) and CuCl catalysis.

Gold-Catalyzed Reaction of ortho-Alkynylarylaldehydes with Conjugated Dienes: An Efficient Access to Highly Strained Tetracyclic Bridgehead Olefins

An unprecedented access to strained tetracyclic bridgehead alkenes by reaction of easily accessible ortho-alkynylarylaldehydes with conjugated dienes is described. The process involves a chemo- and stereo-selective, gold-catalyzed, tandem intermolecular [3+2] cycloaddition/Prins-type ring-closing reaction that allows generating structural complexity in a straightforward manner. This approach for the preparation of anti-Bredt compounds is synthetically superior to those previously reported: the procedure is easy to implement, operates under mild experimental conditions, is efficient, and exhibits a good substrate scope.

Regioselective Synthesis of Polyheterohalogenated Naphthalenes via the Benzannulation of Haloalkynes

Independent control of halide substitution at six of the seven naphthalene positions of 2-arylnaphthalenes is achieved through the regioselective benzannulation of chloro-, bromo-, and iodoalkynes. The modularity of this approach is demonstrated through the preparation of 44 polyheterohalogenated naphthalene products, most of which are difficult to access through known naphthalene syntheses. The outstanding regioselectivity of the reaction is both predictable and proven unambiguously by single-crystal X-ray diffraction for many examples. This synthetic method enables the rapid preparation of complex aromatic systems poised for further derivatization using established cross-coupling methods. The power and versatility of this approach makes substituted naphthalenes highly attractive building blocks for new organic materials and diversity-oriented synthesis.

Bioinspired intramolecular diels-alder reaction: A rapid access to the highly-strained cyclopropane-fused polycyclic skeleton

A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0 2,7]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Mother nature knows best! A gold-catalyzed reaction of enynals and 1,3-dienes, giving rapid access to the highly strained benzotricyclo[3.2.1.02,7]octane skeleton, is reported (see scheme; QMD=quinodimethane). Owing to the mild reaction conditions, excellent substrate scope, and high functional-group tolerance, this system holds potential for the construction of complex molecules with the tricyclo[3.2.1.02,7]octane skeleton. Copyright