Flexible Strategy for Differentially 3,5-Disubstituted 4-Oxypyridin-2(1<i>H</i>)-ones Based on Site-Selective Pd-Catalyzed Cross-Coupling Reactions

Conreaux, David; Bossharth, Emmanuel; Monteiro, Nuno; Desbordes, Philippe; Vors, Jean‐Pierre; Balme, Geneviève

doi:10.1021/ol062721u

Cited by 37 publications

(10 citation statements)

References 24 publications

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“…In recent years, attention has also been directed to the development of site‐selective Suzuki–Miyaura arylation reactions of dihalogenated 2‐pyridones bearing different halogen atoms. As previously mentioned, in 2007, Conreaux et al 95. synthesized 5‐aryl‐3‐bromo‐3‐pyridones 248 as single products in good to excellent yields by Pd(OAc) 2 /TPPTS‐catalyzed reaction of 3‐bromo‐5‐iodo‐4‐methoxy‐ N ‐methylpyridin‐2(1 H )‐one ( 247 ) with a series of arylboronic acids (Scheme ).…”

Section: Cross‐coupling Reactions Of Polyhalogenated Six‐membered Hmentioning

confidence: 96%

“…In 2007, Conreaux et al 95. showed that when 3‐bromo‐5‐iodo‐4‐methoxy‐1‐methylpyridin‐2(1 H )‐one ( 247 ) was reacted with 1.4 equiv.…”

Section: Cross‐coupling Reactions Of Polyhalogenated Six‐membered Hmentioning

confidence: 99%

“…of 4‐chlorophenylboronic acid ( 290a ) in the presence of 4.0 equiv. of K 2 CO 3 in a mixture of toluene and EtOH at 80 °C furnished the unsymmetrically bisarylated pyridone 291 in 81% yield (Scheme ) 95…”

Section: Cross‐coupling Reactions Of Polyhalogenated Six‐membered Hmentioning

confidence: 99%

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Selective Palladium‐Catalyzed Suzuki–Miyaura Reactions of Polyhalogenated Heteroarenes

2012

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The palladium-catalyzed Suzuki-Miyaura reaction of multiply halogenated, electron-rich and electron-deficient heteroarenes is one of the most reliable and environmentally friendly tools for installing a wide range of non-functionalized and functionalized carbon substituents onto heteroaromatic systems with exquisite chemo-and site-selectivity. For substrates with different halogen groups the chemoselectivity of the Suzuki-Miyaura reactions has been found to be dependent on the reactivity difference between the halogens. However, the hardest achievement of selectivity in Suzuki-Miyaura monocouplings involving polyhalogenated heteroarenes with identical halogen atoms has been shown to be dominated by steric and electronic effects and the presence of directing groups at positions neighbouring the reaction sites. Moreover, in the case of symmetrically substituted dihaloheteroarenes with identical halogen atoms, highly selective monocoupling reactions have often been achieved only after a careful optimization of reaction parameters including the catalyst precursor, base, solvent, and the molar ratio between electrophile and organoboron reagent. This critical review with 341 references covers developments on the chemo-and site-selective Suzuki-Miyaura monocoupling reactions of polyhalogenated heteroarenes with different or identical halogen atoms. It also includes the synthesis of polysubstituted heteroarenes, not easily accessible by other means, via consecutive monocoupling reactions and/ or a more synthetically valuable approach involving one-pot polycoupling reactions.

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Section: Cross‐coupling Reactions Of Polyhalogenated Six‐membered Hmentioning

confidence: 96%

“…In 2007, Conreaux et al 95. showed that when 3‐bromo‐5‐iodo‐4‐methoxy‐1‐methylpyridin‐2(1 H )‐one ( 247 ) was reacted with 1.4 equiv.…”

Section: Cross‐coupling Reactions Of Polyhalogenated Six‐membered Hmentioning

confidence: 99%

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Selective Palladium‐Catalyzed Suzuki–Miyaura Reactions of Polyhalogenated Heteroarenes

2012

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“…For example, Gallagher et al ., Balme et al ., and Hibi et al . demonstrated palladium‐catalyzed C3 or C5 selective arylation using the difference in reactivity between aryl halides (I>Br) for synthesis of 3,5‐UDP derivatives (Scheme 1B, eq 1) [5c–f] . In 2004, Baldwin et al .…”

Section: Introductionmentioning

confidence: 99%

Protecting Group‐Controlled Regioselective Synthesis for Unsymmetrical 3,5‐Disubstituted Pyridones

Kwon

Kim

2022

Adv Synth Catal

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Protecting group‐controlled regioselective functionalization of 3,5‐dibromo‐2‐pyridones has been studied for preparation of unsymmetrical 3,5‐disubstituted 2‐pyridones. A bulky di‐tert‐butyl(isobutyl)silyl (BIBS) group was utilized for C5 regioselective arylation in Suzuki‐Miyaura reactions. Meanwhile, the p‐toluenesulfonyl (Ts) group was used to maximize C3 selective halogen‐lithium exchange employing flow chemistry. Most of the reactions proceeded well, with yields of 76 to 95% and excellent regioselectivity. A one‐pot synthesis of unsymmetrical 3,5‐diaryl‐2‐pyridones starting from 3,5‐dibromo‐2‐silyloxypyridine was conducted to demonstrate the practical convenience. Further functionalization onto the remaining bromine group, such as transition metal‐catalyzed C−C and C−N bond‐forming reactions and retro‐Brook rearrangement for C−Si bond formation, was accomplished for synthesis of biologically relevant 3,5‐disubstituted 2‐pyridones. Finally, amrinone and milrinone, commonly used for congestive heart failure, were synthesized in three steps from 3,5‐dibromo‐2‐pyridones in 41% and 56% overall yields, respectively.

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“…Isomeric α‐iodoenamides have also proven to be versatile reagents in Sonogashira and Stille coupling to yield enynamides or dienamides, respectively . Heterocyclic iodoenamides have also been applied in Pd‐catalysed Suzuki–Miyaura and Sonogashira couplings …”

Section: Introductionmentioning

confidence: 99%

A silicon‐assisted synthesis of (E)‐β‐haloenamides from N‐vinylamides

Szudkowska-Frątczak

Zaranek

Hreczycho

et al. 2015

Applied Organom Chemis

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E)-β-Iodoenamides and (E)-β-iodoenimides can be easily obtained from N-vinyl derivatives (N-vinylamides and N-vinylimides) by stereoselective ruthenium-catalysed silylative coupling with vinyltrimethylsilane (Marciniec coupling) and subsequent stereospecific silicon-iodine exchange. Bromodesilylation of (E)-β-silylenimides affords (E)-β-bromoenimides, while the analogous reactions involving (E)-β-silylenamides lead to decomposition of substrates. N-Halosuccinimides have been found as the most effective halogenating agents in the desilylation step under mild conditions. The ruthenium-catalysed silylation/halodesilylation sequence can be performed in a one-pot procedure.

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Flexible Strategy for Differentially 3,5-Disubstituted 4-Oxypyridin-2(1H)-ones Based on Site-Selective Pd-Catalyzed Cross-Coupling Reactions

Cited by 37 publications

References 24 publications

Selective Palladium‐Catalyzed Suzuki–Miyaura Reactions of Polyhalogenated Heteroarenes

Selective Palladium‐Catalyzed Suzuki–Miyaura Reactions of Polyhalogenated Heteroarenes

Protecting Group‐Controlled Regioselective Synthesis for Unsymmetrical 3,5‐Disubstituted Pyridones

A silicon‐assisted synthesis of (E)‐β‐haloenamides from N‐vinylamides

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