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Allylamines are important building blocks in the synthesis of bioactive compounds. The direct coupling of allylic C-H bonds and commonly available amines is a major synthetic challenge. An allylic C-H amination of 1,4-dienes has been accomplished by palladium catalysis. With aromatic amines, branch-selective allylic aminations are favored to generate thermodynamically unstable Z-allylamines. In addition, more basic aliphatic cyclic amines can also engage in the reaction, but linear dienyl allylic amines are the major products.
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http://dx.doi.org/10.1002/anie.202211631 | DOI Listing |
J Org Chem
August 2025
Graduate School of Pharmaceutical Sciences, Kyoto University, Kyoto 606-8501, Japan.
Transformation of allylic C-H bonds into C-C bonds in a regioselective manner represents a powerful approach to generating complex molecules from simple starting materials. Herein, we report a protocol for net δ-C-H alkylation of allyl alcohols involving a sequential azo-ene reaction and an attendant Ni-catalyzed allylic substitution with Grignard reagents. This two-step strategy enables the regioselective alkylation of distal C-H bonds, a transformation that remains challenging via direct approaches under transition-metal catalysis.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Roger Adams Laboratory, Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.
-alkyl arylamines are important structural motifs in pharmaceuticals, yet traditional alkylating methods rely on the nucleophilicity of the amine and make access to such compounds with valuable bioproperties challenging. While metal-mediated reactions may alleviate these limitations, they often encounter amine-metal interactions that can hinder catalysis or lead to deleterious pathways. Herein, we report a palladium(II) [Pd(II)]/sulfoxide-oxazoline(SOX)/phosphoric acid-mediated C(sp)H/N(sp) cross-coupling of 53 arylamine nucleophiles and 39 terminal olefins to furnish >80 diverse tertiary (3°) arylamines in excellent yields (average 82%) and selectivities (>20:1 /, >20:1 linear/branched).
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Bipolarolides A and B are members of the ophiobolin family of sesterterpenes, characterized by their intricate cage-like structures. Herein we report a concise asymmetric total synthesis of bipolarolides A and B enabled by the type-II Diels-Alder reaction. The synthesis features a sequence of key transformations: an iridium-catalyzed enantioselective allylation to establish the first stereocenter, type-II Diels-Alder reaction to rapidly assemble the bicyclo[3.
View Article and Find Full Text PDFChem Commun (Camb)
August 2025
School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, P. R. China.
We report a cobalt-catalyzed C-H functionalization strategy for the modular alkylation and allylation of 2-arylthiazoles using maleimides or allyl acetates as coupling partners. This protocol enables efficient, -selective C-H bond transformations in a single step, providing a broad range of functionalized thiazole derivatives. The developed methodology offers a novel and versatile platform for the direct C-H alkylation and allylation of 2-arylthiazole scaffolds, characterized by operational simplicity, a wide substrate scope, and high tolerance toward diverse functional groups.
View Article and Find Full Text PDFNatl Sci Rev
August 2025
Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Achieving sustainable catalytic transformations requires synergistic optimization of solvent systems, catalytic motifs and energy inputs. Herein, we report a synergistic Pd/hydroquinone catalytic system that enables aerobic allylic C-H functions under ambient conditions (room temperature to 50°C, air) with high turnover frequency (TOF), using ethanol/water as a green medium. This strategy achieves unparalleled synthetic efficiency and demonstrates remarkable versatility across two pivotal transformations (alkylation and amination) involving over 90 products (up to 96% yield).
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