Pd/Cu‐Catalyzed Direct Alkenylation of Azole Heterocycles with Alkenyl Halides

Sahnoun, Sophian; Messaoudi, Samir; Brion, Jean‐Daniel; Alami, Mouâd

doi:10.1002/ejoc.201000959

Cited by 60 publications

(18 citation statements)

References 43 publications

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“…In pursuit of our efforts to extend further the scope of the functionalization of heteroaromatics through C–H bond activation, combined with our interest in discovering new hsp90 inhibitors,22,23 we have developed highly efficient and versatile Pd/Cu‐catalyzed C–H alkenylation reactions of a wide range of azoles. A catalyst system composed of Pd(acac) 2 /CuI/P( o ‐tolyl) 3 in THF in the presence of t BuOLi enables high‐yielding reactions with heterocycles, including the xanthines 28 , the adenines 26 , benzimidazoles, benzoxazoles, benzothiazoles, and thiazoles (Scheme ) 24. The substrate scope of the reaction turned out to be very broad, in terms not only of the azoles but also of a variety of mono‐, di‐, or trisubstituted alkenyl bromides.…”

Section: Direct Intermolecular Alkenylationmentioning

confidence: 99%

Highly Modular POP Ligands for Asymmetric Hydrogenation: Synthesis, Catalytic Activity, and Mechanism

Fernández‐Pérez

Donald

Munslow

et al. 2010

Chemistry A European J

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A library of enantiomerically pure P-OP ligands (phosphine-phosphite), straightforwardly available in two synthetic steps from enantiopure Sharpless epoxy ethers is reported. Both the alkyloxy and phosphite groups can be optimized for maximum enantioselectivity and catalytic activity. Their excellent performance in the Rh-catalyzed asymmetric hydrogenation of a wide variety of functionalized alkenes (26 examples) and modular design makes them attractive for future applications. The lead catalyst incorporates an (S)-BINOL-derived (BINOL = 1,1'-bi-2-naphthol) phosphite group with computational studies revealing that this moiety has a dual effect on the behavior of our P-OP ligands. On one hand, the electronic properties of phosphite hinder the binding and reaction of the substrate in two out of the four possible manifolds. On the other hand, the steric effects of the BINOL allow for discrimination between the two remaining manifolds, thereby elucidating the high efficiency of these catalysts.

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Section: Direct Intermolecular Alkenylationmentioning

confidence: 99%

Highly Modular POP Ligands for Asymmetric Hydrogenation: Synthesis, Catalytic Activity, and Mechanism

Fernández‐Pérez

Donald

Munslow

et al. 2010

Chemistry A European J

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“…For example, C8 arylation reactions of xanthines with aryl halides have been conducted using CuI 6 or Pd(acac) 2 /CuI, 7 and C–H/C–H cross-coupling of xanthines has been accomplished using Pd(OAc) 2 /Cu(OAc) 2 . 8 N9-alkyl adenine derivatives have been subjected to C8 arylation reactions with aryl halides using Pd(OH) 2 /CuI.…”

Section: Introductionmentioning

confidence: 99%

Purinyl N1-Directed Aromatic C–H Oxidation in 6-Arylpurines and 6-Arylpurine Nucleosides

et al. 2013

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Palladium-catalyzed C–H bond activation and oxidation of C6 arylpurines as well as C6 arylpurine nucleosides can be accomplished using Pd(OAc)2/PhI(OAc)2 in CH3CN. Despite the presence of four nitrogen atoms in the purine moiety as well as the polyoxygenated saccharide and a labile glycosidic bond in the nucleosides, these reactions can be effectively conducted. Notably, the generally more labile 2′-deoxyribonucleosides also undergo reaction. The reaction conditions can be tuned to yield either monoacetoxylated or diacetoxylated products predominantly. In the course of these investigations, a dimeric PdII-containing cyclopalladated C6 naphthylpurine derivative has been obtained and crystallographically characterized. This compound is competent in catalyzing the oxidization with PhI(OAc)2, indicating its plausible intermediacy in the chemistry. The X-ray structure of a monoacetoxylated product from this reaction has also been obtained.

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“…Analogous Pd/Cu-mediated C8 alkenylations of 6-(benzylthio)-9- N -benzylpurines with styryl bromides provided access to 6,8,9-trisubstituted purines [45]. The optimized conditions (Pd/CuI/ t BuOLi) were applicable for the selective alkenylation of caffeine, benzimidazole and other aromatic azole heterocycles [45,46]. These are significant developments since it was reported that 8-bromoadenosine was not a good substrate for Mizoroki-Heck reaction [47] making modification at 8 position via direct functionalization of C8-H bond a desirable transformation.…”

Section: Direct Activation Of C8-h Bond In Purine and Purine Nuclementioning

confidence: 99%

Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

Liang

Wnuk

2015

Molecules

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Transition metal-catalyzed modifications of the activated heterocyclic bases of nucleosides as well as DNA or RNA fragments employing traditional cross-coupling methods have been well-established in nucleic acid chemistry. This review covers advances in the area of cross-coupling reactions in which nucleosides are functionalized via direct activation of the C8-H bond in purine and the C5-H or C6-H bond in uracil bases. The review focuses on Pd/Cu-catalyzed couplings between unactivated nucleoside bases with aryl halides. It also discusses cross-dehydrogenative arylations and alkenylations as well as other reactions used for modification of nucleoside bases that avoid the use of organometallic precursors and involve direct C-H bond activation in at least one substrate. The scope and efficiency of these coupling reactions along with some mechanistic considerations are discussed.

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Pd/Cu‐Catalyzed Direct Alkenylation of Azole Heterocycles with Alkenyl Halides

Cited by 60 publications

References 43 publications

Highly Modular POP Ligands for Asymmetric Hydrogenation: Synthesis, Catalytic Activity, and Mechanism

Highly Modular POP Ligands for Asymmetric Hydrogenation: Synthesis, Catalytic Activity, and Mechanism

Purinyl N1-Directed Aromatic C–H Oxidation in 6-Arylpurines and 6-Arylpurine Nucleosides

Modification of Purine and Pyrimidine Nucleosides by Direct C-H Bond Activation

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