The cross-coupling of α-aminoalkyltrifluoroborates and Grignard reagents to form N, N-substituted α-tertiary amines (ATAs) is reported. Key to the success of this reaction is the unexpected oxidation of the α-aminoalkyltrifluoroborate to the corresponding iminium cation by commercially available Barluenga's reagent. Various Grignard reagents added smoothly, enabling the synthesis of a variety of ATAs, which are of high value for medicinal chemistry and drug development. Many of the reported examples are not accessible by the established methods.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.8b01613 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Stereoselective Preparation and Pd-catalyzed Suzuki-Miyaura Cross-coupling of Alkenyl Sulfoximine.
Angew Chem Int Ed Engl
January 2025
Osaka University: Osaka Daigaku, Department of Applied Chemistry, JAPAN.
Although numerous transition-metal catalyzed cross-coupling reactions of alkenyl electrophiles with a sulfur(VI) leaving group, mainly alkenyl sulfones, have been developed, most rely heavily on highly nucleophilic Grignard reagents, and the use of organoboron reagents remains challenging. We report herein facile preparation and the following Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of alkenyl sulfoximine, a monoaza analog of sulfone. The condensation of alkyl sulfoximine with aldehydes, developed in this study, makes alkenyl sulfoximines more readily available.
View Article and Find Full Text PDFTrinuclear Borane (BH)-Mediated Selective C4-H Alkylation and Phosphonation of Quinolines and Tetrahydroquinolines.
Org Lett
January 2025
College of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001, China.
Herein, we report a method for the regioselective alkylation and phosphonation of quinoline C4-H via a BH-mediated nucleophilic addition of Turbo Grignard reagents and phosphine oxide anions to quinolines bearing different substituents, affording the 4-alkyl and 4-phosphoryl quinolines and tetrahydroquinolines after one-pot oxidation or reduction. The results indicate that coordination of the BH group can activate substrates toward a potential 1,4-dearomative addition and subtly control the regioselectivity by preventing the 1,2-dearomative addition.
View Article and Find Full Text PDFIon Hydration Enables Generality in Asymmetric Catalysis: Desymmetrization to P-Stereogenic Triarylphosphine Derivatives.
Angew Chem Int Ed Engl
December 2024
Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 2, Singapore, 117543, Singapore.
Asymmetric synthesis relies on seamless transmission of stereochemical information from a chiral reagent/catalyst to a prochiral substrate. The disruption by substrates' structural changes presents a hurdle in innovating generality-oriented asymmetric catalysis. Here, we report a strategy for substrate adaptability by exploiting a fundamental physicochemical phenomenon-ion hydration, in developing remote desymmetrization to access P-stereogenic triarylphosphine oxides and sulfides.
View Article and Find Full Text PDFConvenient lanthanum-mediated synthesis of bulky -alkyl amines from nitriles.
Chem Commun (Camb)
December 2024
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
-alkyl amines can be conveniently prepared in one step from nitriles by a double addition of ethyl or propyl Grignard reagent mediated by a commercially available lanthanum chloride-lithium chloride complex solution. The reaction operates on a variety of benzonitriles, with several heterocyclic nitriles and an alkyl nitrile also being suitable substrates.
View Article and Find Full Text PDFSynthesis of Consecutive All-Carbon Quaternary Centers via Three-Step Reactions.
Org Lett
December 2024
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki Aza-Aoba, Aoba-ku, Sendai, Miyagi 980-8578, Japan.
Consecutive all-carbon quaternary centers were synthesized in three steps from the corresponding ketones. The three reactions were (1) Knoevenagel condensation of ketone and malononitrile to afford dicyanoalkene, (2) 1,4-addition reaction of a Grignard reagent to dicyanoalkene, and (3) oxidative transformation of a malononitrile moiety to an ester, thioester, amide, and α-nitroketone. This method was applied to the synthesis of 17α-methyl steroids with a good yield and excellent diastereoselectivity.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!