- Robust alkyl-bridged bis(N-heterocyclic carbene)palladium(II) complexes anchored on Merrifield's resin as active catalysts for the selective synthesis of flavones and alkynones
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Highly active and efficient propylene-bridged bis(N-heterocyclic carbene)palladium(II) complexes covalently anchored on Merrifield's resin were synthesized and characterized using various physical and spectroscopic techniques. The two anchored Pd(II) complexes consist of the system: Merrifield's resin-linker-bis(NHC)Pd(II), the linkers being benzyl and benzyl-O-(CH2)3 for (Pd-NHC1@M) and (Pd-NHC2@M), respectively. The short linker anchored bis-benzimidazolium ligand precursor (PBBI-1@M) was synthesized via direct carbon–nitrogen alkylation of a propylene-bridged bis(benzimidazole) (PBBI-1) by Merrifield's resin chlorobenzyl group. The longer linker anchored bis-benzimidazolium ligand precursor (PBBI-2@M) was obtained in a two-step reaction involving first alkylation of (PBBI-1) with 3-chloro-1-propanol followed by a nucleophilic substitution at Merrifield's resin chlorobenzyl group. Both supported ligand precursors (PBBI-1@M and PBBI-2@M) reacted with palladium acetate to produce the two heterogeneous catalysts (Pd-NHC1@M) and (Pd-NHC2@M). 13C NMR palladation shift of the benzimidazole N–C–N (C2) carbon was found very similar in both the liquid NMR spectra of the homogeneous complexes and the CP/MASS spectra of the corresponding covalently anchored complexes. The catalytic activity, stability, and the recycling ability of the supported catalysts have been investigated in the carbonylative Sonogashira coupling reactions of aryl iodides with aryl alkynes and alkyl alkynes and also in the cyclocarbonylative Sonogashira coupling reactions of aryl iodides with aryl alkynes via one pot reactions. The longer linker catalyst Pd-NHC2@M demonstrated excellent catalytic activity, stability, and very high recycling ability in the two carbonylative coupling reactions. These systems exhibit the hypothesized thermodynamic stability offered by the chelate effect in addition to the strong sigma donor ability of a bis(NHC) ligand system generating electron-rich palladium centers that favor the oxidative addition step of the aryl halide.
- Mansour, Waseem,Fettouhi, Mohammed,Saleem, Qasim,El Ali, Bassam
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- Divergent synthesis of flavones and aurones via base-controlled regioselective palladium catalyzed carbonylative cyclization
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A regioselective approach for construction of 5-membered and 6-membered flavonoid is established by Pd catalyzed carbonylative cyclization of 2-iodophenol with terminal alkynes using different amine bases under mild reaction condition. The catalytic experiments found that piperazine preferentially accelerate 6-endo cyclization, and triethylamine mediated Pd catalyzed 5-exo cyclization. Under optimized reaction condition, Pd catalyzed carbonylative protocol successfully applied for the diverse structures of 39 examples in good to excellent yield and regioselectivity.
- Xu, Shan,Sun, Huaming,Zhuang, Mengyuan,Zheng, Shaohua,Jian, Yajun,Zhang, Weiqiang,Gao, Ziwei
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p. 264 - 270
(2018/05/04)
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- Synthesis of pinacol arylboronates from aromatic amines: A metal-free transformation
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A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.
- Qiu, Di,Jin, Liang,Zheng, Zhitong,Meng, He,Mo, Fanyang,Wang, Xi,Zhang, Yan,Wang, Jianbo
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p. 1923 - 1933
(2013/03/29)
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- Optimized palladium(0)-catalyzed Suzuki cross-coupling reaction of polystyrene-supported selenenyl flavanones: A convenient preparation of biaryl-chromen-4-one
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Application of the Suzuki cross-coupling reaction for efficient synthesis of diverse substituted biaryl-chromen-4-ones using an optimized palladium(0) catalyst system is reported. The coupling of arylboronic acids with the resin-bound bromoflavanones whic
- Tang,Li, Wen,Gao, Zhangyong,Zhang, Lianpeng,Ma, Qiushi
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experimental part
p. 585 - 589
(2012/05/19)
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- Microwave enhanced palladium catalysed coupling reactions: A diversity-oriented synthesis approach to functionalised flavones
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Microwave enhanced diversity-oriented synthesis (MEDOS) using palladium catalysed protocols is introduced as a powerful new strategy for the synthesis of systematically modified small molecules and is highlighted by application to functionalised flavones. The Royal Society of Chemistry 2006.
- Fitzmaurice, Richard J.,Etheridge, Zac C.,Jumel, Emelie,Woolfson, Derek N.,Caddick, Stephen
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p. 4814 - 4816
(2007/10/03)
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- SYNTHESIS OF 6- AND 8-PHENYL-SUBSTITUTED FLAVONOIDS.
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3-Acetylbiphenyl-4-ol and -2-ol were condensed with substituted benzaldehydes to give respectively 5 prime - and 3 prime -phenyl-substituted chalcones which were cyclized to afford 6- and 8-phenylflavanones. The chalcones also gave the corresponding 6- an
- Matsumura,Tsuchiya,Takeda,Imafuku
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p. 2037 - 2043
(2007/10/02)
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