Palladium-Catalyzed Cross-Coupling of Sterically Demanding Boronic Acids with α-Bromocarbonyl Compounds

Zimmermann, Bettina; Dzik, Wojciech I.; Himmler, Thomas; Gooßen, Lukas J.

doi:10.1021/jo2014998

Cited by 28 publications

(8 citation statements)

References 31 publications

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“…This catalytic form is usually generated in situ and participates in the polymerization reaction, [31] and the organometallic species changes. [32,33] Furthermore, the catalytic mixture of Pd 2 (dba) 3 and tris(o-tolyl)phosphine is used regularly in coupling reactions [34] to generate catalytic species (undefined catalyst form). Two p-substituted stilbene derivatives (16 and 17) were used for the catalytic screening of Suzuki coupling catalyzed by 1.…”

Section: Resultsmentioning

confidence: 99%

A Highly Stereoselective and Efficient Catalytic Approach for the Synthesis of trans‐Stilbene–Arenes as π‐Conjugated Materials

2017

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The potential expansion of the variety of catalytic methods for carbon–carbon bond formation is explored in many research centers all over the world. In this work, we describe very precise and controlled catalytic transformations as useful tools for the synthesis of new trans‐π‐conjugated molecular organic compounds. The combination of Suzuki–Miyaura coupling and cross‐metathesis reactions is established as a simple and efficient method for the design of new (E)‐stilbenes in the presence of well‐defined transition‐metal catalysts at 0.0001–1 % loadings. All of the desired products are isolated in good‐to‐excellent yields (up to 96 % isolated yield) with high purity.

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Section: Resultsmentioning

confidence: 99%

A Highly Stereoselective and Efficient Catalytic Approach for the Synthesis of trans‐Stilbene–Arenes as π‐Conjugated Materials

2017

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“…After optimization of the catalytic system, the reaction was extended to sterically demanding ortho-substituted boronic acids. 19 With these coupling partners, the use of a catalytic amount of Pd(dba) 2 (0.3 mol%) together with P(otol) 3 (0.9 mol%) in the presence of a phase transfer agent BnN + (Et) 3 Brand a base (KF) exhibited the best performance, allowing the isolation of 2.7 in a good yield (58%) (Scheme 6).…”

Section: Scheme 5 α-Arylation Of Secondary and Tertiary Amides From αmentioning

confidence: 99%

α-Arylation of Amides from α-Halo Amides Using Metal-Catalyzed Cross-Coupling Reactions

Barde¹,

Guérinot

Cossy

2018

Synthesis

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Metal-catalyzed α-arylation of amides from α-halo amides with organometallic reagents is reviewed. The article includes Suzuki–Miyaura, Kumada–Corriu, Negishi, and Hiyama cross-coupling reactions.1 Introduction2 Suzuki–Miyaura Cross-Coupling2.1 Palladium Catalysis2.2 Nickel Catalysis3 Kumada–Corriu Cross-Coupling3.1 Nickel Catalysis3.2 Iron Catalysis3.3 Cobalt Catalysis4 Negishi Cross-Coupling5 Hiyama Cross-Coupling6 Conclusion

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“…cis-2-tert-Butyl-5-(2-pyridyl)-1,3-dioxane (15): white solid; mp 44.8−45.4 °C (pentane); 1 H NMR (400 MHz, CDCl 3 ) δ 0.92 (s, 9H), 2.78−2.82 (br m, 1H), 4.17 cis-2-tert-Butyl-5-(2-pyridyl)-1,3-dioxane Hydrobromide (17). A solution of 125 mg (0.56 mmol) of 15 and 387 mg (2.82 mmol) of freshly distilled tert-butyl bromide in 2.5 mL of dry CHCl 3 was heated at reflux for 12 h and then allowed to cool to room temperature.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Controlling the Conformational Energy of a Phenyl Group by Tuning the Strength of a Nonclassical CH···O Hydrogen Bond: The Case of 5-Phenyl-1,3-dioxane

et al. 2016

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Anancomeric 5-phenyl-1,3-dioxanes provide a unique opportunity to study factors that control conformation. Whereas one might expect an axial phenyl group at C(5) of 1,3-dioxane to adopt a conformation similar to that in axial phenylcyclohexane, a series of studies including X-ray crystallography, NOE measurements, and DFT calculations demonstrate that the phenyl prefers to lie over the dioxane ring in order to position an ortho-hydrogen to participate in a stabilizing, nonclassical CH···O hydrogen bond with a ring oxygen of the dioxane. Acid-catalyzed equilibration of a series of anancomeric 2-tert-butyl-5-aryl-1,3-dioxane isomers demonstrates that remote substituents on the phenyl ring affect the conformational energy of a 5-aryl-1,3-dioxane: electron-withdrawing substituents decrease the conformational energy of the aryl group, while electron-donating substituents increase the conformational energy of the group. This effect is correlated in a very linear way to Hammett substituent parameters. In short, the strength of the CH···O hydrogen bond may be tuned in a predictable way in response to the electron-withdrawing or electron-donating ability of substituents positioned remotely on the aryl ring. This effect may be profound: a 3,5-bis-CF phenyl group at C(5) in 1,3-dioxane displays a pronounced preference for the axial orientation. The results are relevant to broader conformational issues involving heterocyclic systems bearing aryl substituents.

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Palladium-Catalyzed Cross-Coupling of Sterically Demanding Boronic Acids with α-Bromocarbonyl Compounds

Cited by 28 publications

References 31 publications

A Highly Stereoselective and Efficient Catalytic Approach for the Synthesis of trans‐Stilbene–Arenes as π‐Conjugated Materials

A Highly Stereoselective and Efficient Catalytic Approach for the Synthesis of trans‐Stilbene–Arenes as π‐Conjugated Materials

α-Arylation of Amides from α-Halo Amides Using Metal-Catalyzed Cross-Coupling Reactions

Controlling the Conformational Energy of a Phenyl Group by Tuning the Strength of a Nonclassical CH···O Hydrogen Bond: The Case of 5-Phenyl-1,3-dioxane

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