This study introduces a novel approach involving XB-mediated cross-coupling of α-trifluoromethylated alkyl bromides with coumarins and quinolinones under visible light irradiation. Both density functional theory (DFT) calculations and experimental studies converge to suggest that the noncovalent interaction between alkyl bromides and DMAP, intensified by the α-trifluoromethyl group, plays a pivotal role in facilitating this chemoselective reaction.
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http://dx.doi.org/10.1021/acs.orglett.4c00717 | DOI Listing |
J Am Chem Soc
January 2025
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
The direct synthesis of C(sp)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there is a strong impetus to develop new methods by which to access sp-rich molecules from commercial feedstocks, such as alkenes.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal 462066, MP, India.
We report herein a palladium-catalyzed distal alkylation of silyldienol and silyltrienol ethers of enones through coupling with activated halides to achieve new - and -alkylated motifs. Additionally, by employing propargyl bromides, synthetically useful linear allenes along with functionalized enones have been synthesized. Low-catalyst loading, and late-stage transformations of pharmaceutically relevant molecules further showcase the importance of the present protocol.
View Article and Find Full Text PDFChem Sci
December 2024
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Hubei University Wuhan 430062 P. R. China
The prevalence of naphthalene compounds in biologically active natural products, organic ligands and approved drugs has motivated investigators to develop efficient strategies for their selective synthesis. C-H functionalization of naphthalene has been frequently deployed, but mainly involves two-component reactions, while multiple-component C-H functionalization for the synthesis of naphthalene compounds has thus far proven elusive. Herein, we disclose a versatile three-component protocol for the modular synthesis of multifunctional naphthalenes from readily available simple naphthalenes, olefins and alkyl bromides P(iii)-assisted ruthenium-catalyzed remote C-H functionalization.
View Article and Find Full Text PDFHeliyon
December 2024
Curia Wisconsin, Inc. D/B/A Siegfried Acceleration Hub, 870 Badger Circle, Grafton, WI, 53024, United States.
Primary and secondary alkyl iodides and primary alkyl bromides were quickly and conveniently converted into their corresponding alkyl chlorides via S2 halide-halide substitution. The resultant alkyl chlorides simultaneously demonstrated increased volatility and stability paired with standard headspace GC-FID methodology. The derivatization was performed on both standard and sample alike and occurred during the headspace oven equilibration phase, eliminating the extra reaction step traditionally performed during many derivatization analyses.
View Article and Find Full Text PDFThe development of new protocols for stereospecific and stereoselective halogenation transformations by mild reaction conditions is a highly desirable research target for the chemical and pharmaceutical industries. Following the straightforward methodology for directly transforming a wide scope of alcohols to alkyl bromides and chlorides using substoichiometric amounts of thioureas and N-halo succinimides (NXS) as a halogen source in a single step, we noticed that in apolar solvents bromination of chiral secondary alcohols did not produce the expected racemates. In this study, the stereochemical aspects of the bromination reaction were examined.
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