RESUMO
Highly substituted benzene derivatives, including alkoxy-, iodoalkoxy-, and diiodo-substituted benzenes, can be selectively synthesized via Brønsted acid catalyzed and iodine-promoted tandem carbocyclization respectively. This reaction involved a direct process for C-C bond formation from 5,2-enyn-1-ones, and different reaction systems (Brønsted acids/electrophiles with solvents) afforded different substituted benzenes. Furthermore, the halogenated moiety and alkoxy group can be readily introduced into the benzene in a position which has not been easily obtained previously.
Assuntos
Ácidos/química , Alcenos/química , Alcinos/química , Benzeno/síntese química , Iodo/química , Cetonas/química , Benzeno/química , Catálise , Ciclização , Estrutura MolecularRESUMO
Functionalized 3,4-dihalogenated furan-2(5H)-ones can be readily prepared in moderate to good yields by treating 4-hydroxy-4-arylbut-2-ynoate derivatives with ICl, IBr, and I(2). Both halogen atoms of the electrophile are incorporated in the product. The resulting halides can further afford polycyclic aromatic compounds using known palladium-catalyzed coupling reactions.
Assuntos
Furanos/química , Alcinos/química , Catálise , Ciclização , Furanos/síntese química , Halogênios/química , Paládio/química , Propanóis/químicaAssuntos
Alcinos/química , Pironas/síntese química , Catálise , Ciclização , Estrutura Molecular , Pironas/química , EstereoisomerismoRESUMO
A method for preparing five- or six-membered heterocyclic compounds from enyne carbonates via palladium catalysis was developed. Enyne carbonates were transformed into 3-vinylidene-1-tosylpyridines 2 in the presence of PdI(2) as the catalyst. Using Pd(dba)(2) as the catalyst, 3-vinylidene-1-tosylpyrrolidines 3 were obtained. Further functionalizations of compounds 3 were carried out in a one-pot manner.
RESUMO
Highly substituted indole derivatives bearing alkyl and aryl moieties can be prepared by Sc(OTf)(3)-catalyzed Friedel-Crafts alkenylation of 5-(arylamino)pent-3-yn-2-ones. In addition, a method for regioselective hydrochlorination of 5-(arylamino)pent-3-yn-2-ones mediated by SnCl(4) in moderate to good yields (up to 84%) has been developed. The resulting exclusive Z-selectivity of the C-Cl bond can be further exploited using cross C-N coupling reactions.
Assuntos
Química Farmacêutica/métodos , Indóis/síntese química , Cetonas/química , Mesilatos/química , Escândio/química , Compostos de Estanho/química , Catálise , Halogenação , Indóis/análise , Espectroscopia de Ressonância Magnética , Estrutura Molecular , EstereoisomerismoRESUMO
Highly substituted 3-iodoquinolines bearing different alkyl and aryl moieties can be synthesized in moderate to excellent yields (up to 99%) by 6-endo-dig iodocyclization of 2-tosylaminophenylprop-1-yn-3-ols with molecular iodine (I(2)) under mild conditions. The cyclization is highly regioselective and the resulting 3-iodoquinolines can be further functionalized by various coupling reactions.
Assuntos
Hidrocarbonetos Iodados/síntese química , Quinolinas/síntese química , Catálise , Ciclização , Hidrocarbonetos Iodados/química , Iodo/química , Estrutura Molecular , Quinolinas/química , EstereoisomerismoRESUMO
A novel and convenient carboannulation method for the synthesis of highly substituted naphthylamine derivatives has been developed though a Pd(0)-catalyzed [1,5]-sigmatropic hydrogen shift and cyclization reaction of propargyl esters.
RESUMO
Diiodinated carbocycles and oxygen heterocycles can be readily synthesized by electrophilic carbocyclization of aryl propargylic alcohols in moderate to good yields under mild conditions. The resulting diiodide can be further exploited by subsequent oxidizing and coupling reactions. Both the iodine anion and cation generated from I(2) are used effectively. The presence of a trace amount of water is essential for this electrophilic cyclization.
RESUMO
A mild and direct pathway for the formation of five-membered heterocyclic compounds from hydroxylated enynes has been developed. In this reaction, hydroxylated enynes were selectively transformed into five-membered heterocyclic compounds 2, with an allene moiety at the 3-position, in the presence of F(3) CSO(3) H (0.1â mol %). When R(1) , R(2) =Ph, diphenylvinyl-2,3-dihydro-1H-pyrrole (2 y) was obtained. With HSbF(6) (5â mol %) as the catalyst, polycyclic skeletons 3 and 4 with adjacent stereocenters were obtained. When R(1) =H and R(2) =styrene, 1,3-dienyl-2,5-dihydro-1H-pyrrole (6 as) was formed. This Brønsted acid catalyzed domino process involves the formation of an allene carbocation intermediate, which can be readily trapped by olefins to give various novel five-membered heterocyclic skeletons.
Assuntos
Alcadienos/síntese química , Alcinos/síntese química , Pirróis/síntese química , Alcadienos/química , Alcenos/química , Alcinos/química , Catálise , Técnicas de Química Combinatória , Cristalografia por Raios X , Ciclização , Estrutura Molecular , Pirróis/químicaRESUMO
The synthesis of 3-(aminoalkyl)coumarins starting with a platinum/scandium-cocatalyzed oxidative dehydrogenation of α,ß-C(sp(3))-H bonds of tertiary amines in the presence of ambient oxygen followed by reactions with substituted salicylaldehydes is revealed. The in situ formed enamines reacted with various salicylaldehydes, which resulted in the development of a one-pot synthetic protocol involving aldol reaction, cyclization, and then ring-opening.
Assuntos
Aldeídos/química , Compostos Alílicos/síntese química , Cumarínicos/síntese química , Platina/química , Escândio/química , Compostos Alílicos/química , Cumarínicos/química , Ciclização , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Oxirredução , EstereoisomerismoRESUMO
A mild, metal-free, and environmently benign iodine-promoted regioselective C-C and C-N bonds formation of N-protected indole derivatives giving 2,3'-biindoles 2 and 4-(1H-indol-2-yl)morpholines 4 is successfully demonstrated. Various bioactive 2,3'-biindoles and 4-(1H-indol-2-yl)morpholines, bearing electron-rich to moderately electron-poor substituents, can be prepared in moderate to good yields.
Assuntos
Indóis/química , Iodo/química , Morfolinas/química , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Estrutura Molecular , EstereoisomerismoRESUMO
Highly substituted dihalogenated dihydrofurans, dihydropyrroles, and dihydro-2H-pyrans bearing alkyl, vinyl, aryl, and heteroaryl moieties can be prepared in good to excellent yields (up to 99%) by allowing 1,4-butyne-diol, 4-aminobut-2-yn-1-ol, and pent-2-yne-1,5-diol derivatives to react with different electrophiles (I(2), IBr, and ICl) at room temperature. Both halogen atoms generated from electrophiles were used effectively. The resulting halides can be further exploited by using palladium-catalyzed coupling reactions. The presence of trace amount of water is essential for this electrophilic cyclization.
Assuntos
Furanos/síntese química , Compostos Heterocíclicos/síntese química , Piranos/síntese química , Pirróis/síntese química , Cristalografia por Raios X , Ciclização , Furanos/química , Compostos Heterocíclicos/química , Modelos Moleculares , Estrutura Molecular , Piranos/química , Pirróis/química , EstereoisomerismoRESUMO
A third strategy for cross-dehydrogenative coupling reaction has been reported via platinum-catalyzed sp(3) C-H and sp(3) C-H coupling reaction in the absence of oxidant. Nitroalkanes as well as dialkyl malonate derivatives, beta-keto esters and malononitrile are active participants in this coupling reaction. Both cyclic and acyclic non-activated simple ketones are good reactants in this reaction.
Assuntos
Alcanos/química , Ésteres/química , Cetonas/síntese química , Nitrilas/química , Nitrocompostos/química , Platina/química , Catálise , Hidrogenação , Cetonas/química , Estrutura Molecular , Oxirredução , EstereoisomerismoRESUMO
A mild platinum-catalyzed oxidative dehydrogenation of alpha,beta-C(sp(3))-H bonds of tertiary amines in the presence of ambient oxygen is revealed, and the in situ formed enamines subsequently reacting with various nitroolefins resulted in the development of two one-pot synthetic protocols involving Michael addition-elimination and Michael addition-cyclization. By using different functionalized nitroolefins compatible with the current oxidative conditions, two types of structurally divergent products, trisubstituted enamines and chromano[2,3-b]piperidines, could be expediently accessed, respectively.
RESUMO
A PhI(OAc)(2) mediated selective functionalization of sp(3) C-H bonds adjacent to a nitrogen atom has been reported. When piperidine derivates were used, direct diacetoxylation of alpha and beta sp(3) C-H adjacent to a nitrogen atom were observed to afford various cis-2,3-diacetoxylated piperidines. On the other hand, tetrahydroisoquinoline derivatives gave various alpha-C-H functionalized products in the presence of PhI(OAc)(2). Nitroalkanes, dialkyl malonates, and beta-keto ester are active participants in this coupling reaction. Meanwhile, alpha-amino nitriles can also be obtained by oxidative coupling of amines with malononitrile.
RESUMO
A mild and direct process for C-C bond formation from propargylic alcohols and olefin has been developed in the presence of a silver catalyst. In this reaction, trace amounts of water were necessary and allene alcohols 2 and 1,3-dienes 3 were obtained selectively.
Assuntos
Alcenos/química , Alcinos/química , Carbono/química , Propanóis/química , Antimônio/química , Catálise , Cristalografia por Raios X , Ciclização , Estrutura Molecular , Prata/químicaRESUMO
The acid-catalyzed reaction of epoxy alkyne involves an epoxide ring-opening attacked by pi-alkyne, leading to a semipinacol-type rearrangement. In this process, a type of carbon-carbon 3,3-migration of the alkyne system has been discovered, which is promoted both by epoxide inducing and hydroxide promoting. This transformation enables the fast synthesis of allenes in mild conditions.