Palladium mediated synthesis of isoindolinones and isoquinolinones

Khan, Mohammad Wahiduzzaman; Abdollahi, Reza

doi:10.1016/j.tet.2005.09.032

Cited by 39 publications

(14 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[35] In addition, the direct synthesis of indole from anilines and ketones has been carried out, employing Pd(OAc) 2 with Cu (OAc) 2 as a stoichiometric co-oxidant. [36] In recent years, our group has developed methods for the synthesis of benzo-fused heterocyclic compounds including isoindolines, isoquinolinone, [37] benz[b] furans, [38] and indoles, [39] by palladium-catalyzed reactions of aryl iodide with terminal alkynes. [40] As the substituted indole nucleus is a structural component of a vast number of biologically active and functional materials and natural and synthetic compounds, we are therefore interested in developing a convenient method for the synthesis.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐catalyzed cyclization of 2‐alkynyl‐N‐ethanoyl anilines to indoles: synthesis, structural, spectroscopic, and mechanistic study

Hoque

Halim²,

Sarwar

et al. 2015

J of Physical Organic Chem

Self Cite

View full text Add to dashboard Cite

This study reports a facial regio‐selective synthesis of 2‐alkyl‐N‐ethanoyl indoles from substituted‐N‐ethanoyl anilines employing palladium (II) chloride, which acts as a cyclization catalyst. The mechanistic trait of palladium‐based cyclization is also explored by employing density functional theory. In a two‐step mechanism, the palladium, which attaches to the ethylene carbons, promotes the proton transfer and cyclization. The gas‐phase barrier height of the first transition state is 37 kcal/mol, indicating the rate‐determining step of this reaction. Incorporating acetonitrile through the solvation model on density solvation model reduces the barrier height to 31 kcal/mol. In the presence of solvent, the electron‐releasing (–CH3) group has a greater influence on the reduction of the barrier height compared with the electron‐withdrawing group (–Cl). These results further confirm that solvent plays an important role on palladium‐catalyzed proton transfer and cyclization. For unveiling structural, spectroscopic, and photophysical properties, experimental and computational studies are also performed. Thermodynamic analysis discloses that these reactions are exothermic. The highest occupied molecular orbitallowest unoccupied molecular orbital gap (4.9–5.0 eV) confirms that these compounds are more chemically reactive than indole. The calculated UV–Vis spectra by time‐dependent density functional theory exhibit strong peaks at 290, 246, and 232 nm, in good agreement with the experimental results. Moreover, experimental and computed 1H and 13C NMR chemical shifts of the indole derivatives are well correlated. Copyright © 2015 John Wiley & Sons, Ltd.

show abstract

Section: Introductionmentioning

confidence: 99%

Palladium‐catalyzed cyclization of 2‐alkynyl‐N‐ethanoyl anilines to indoles: synthesis, structural, spectroscopic, and mechanistic study

Hoque

Halim²,

Sarwar

et al. 2015

J of Physical Organic Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…Several synthetic routes have been reported towards isoquinoline nucleus (Awuah & Capretta, 2010;Glushkov & Shklyaev, 2001), including the Gabriel-Colman synthesis via ring enlargement of phthalimides (Delcey et al, 1995), the Curtius rearrangement of azides derived from 2-(2-carboxyethyl)benzoic acids (Mujde, Ozcan, & Balci, 2011), condensation of amines with homophthalic anhydrides (Semple, Rydzewski, & Gardner, 1996), reaction of 2-methoxycarbonylstyrene oxide with ammonia or methylamine (Lin et al, 2003), the [4 þ 2]-cycloaddition of the ketenes to cyano ketones (Minami, Nishimoto, & Hanaoka, 1995), treatment of indanones with sodium azide (Scriven & Turnbull, 1988), solid-phase synthesis Bischler-Napieralski cyclisation (Chern & Li, 2004), palladium mediated synthesis (Khan & Masud Reza, 2005), Vilsmeier-Haack reaction of 3-arylisoquinolines (Khadka, Yang, Cho, Zhao, & Cho, 2011) and reaction of coumarin and isocoumarin derivatives with ammonia and amines. The latter method has been used in the synthesis of (�)-licoricidin (Beccalli et al, 2007), narciclasine (Khaldi et al, 1995), (þ)-deoxypancratistatin (Ohta & Kimoto, 1975) and the benzophenanthridine alkaloid nitidine (Minami et al, 1995).…”

Section: Introductionmentioning

confidence: 99%

An efficient total synthesis of ruprechstyril fromRuprechtia tangarana

Saeed

2013

Natural Product Research

View full text Add to dashboard Cite

A short total synthesis of natural isocarbostyril ruprechstyril (3-n-pentyl-6-methoxy-8-hydroxy-1(2H)-isoquinolinone) isolated from Ruprechtia tangarana is reported. 6,8-Dimethoxy-3-pentylisocoumarin obtained by condensation of 3,5-dimethoxyhomophthalic anhydride with hexanoyl chloride was smoothly converted to O-methylruprechstyril by refluxing with methanamide. Regioselective demethylation of the latter using anhydrous aluminium chloride in dichloromethane furnished the ruprechstyril. Complete demethylation to give (6-desmethoxyruprechstyril) was achieved using same reagent in ethanethiol.

show abstract

“…A synthetic method for obtaining bis(isoindolinones) starting from aryl chlorides in nickel(0)-catalysed reaction was described. 13 Palladium-catalysed reactions of 2-iodo-Nsubstituted benzamides, 14 that of aryl iodides in carbonylationeami nationeMichael addition cascade 15 and that of 2 0 -bromoacetophenone with primary amines under carbon monoxide 16 proved to be highly efficient for the synthesis of the 1-isoindolinone scaffold. Isoindolinones via room temperature palladium nanoparticle-catalysed carbonylationeamination cascade were synthesised.…”

Section: Introductionmentioning

confidence: 99%