7277-86-3Relevant articles and documents
Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature
Tappen, Jens,Rodstein, Ilja,McGuire, Katie,Gro?johann, Angela,L?ffler, Julian,Scherpf, Thorsten,Gessner, Viktoria H.
supporting information, p. 4281 - 4288 (2020/03/13)
Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy3P+?C?(R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3P+?C?(Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C?N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down β-hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C?N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram-scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h?1.
PREPARATION OF SECONDARY AMINES WITH ELECTROPHILIC N-LINCHPIN REAGENTS
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Page/Page column 101-102, (2018/12/13)
In one aspect, the present disclosure provides methods of preparing a secondary amine. In some embodiments, the secondary amine comprises two different groups or two identifical groups. Also provided herein are compositions for use in the preparation of the secondary amine.
Practical Singly and Doubly Electrophilic Aminating Agents: A New, More Sustainable Platform for Carbon-Nitrogen Bond Formation
Kattamuri, Padmanabha V.,Yin, Jun,Siriwongsup, Surached,Kwon, Doo-Hyun,Ess, Daniel H.,Li, Qun,Li, Guigen,Yousufuddin, Muhammed,Richardson, Paul F.,Sutton, Scott C.,Kürti, László
supporting information, p. 11184 - 11196 (2017/08/21)
Given the importance of amines in a large number of biologically active natural products, active pharmaceutical ingredients, agrochemicals, and functional materials, the development of efficient C-N bond-forming methods with wide substrate scope continues to be at the frontier of research in synthetic organic chemistry. Here, we present a general and fundamentally new synthetic approach for the direct, transition-metal-free preparation of symmetrical and unsymmetrical diaryl-, arylalkyl-, and dialkylamines that relies on the facile single or double addition of readily available C-nucleophiles to the nitrogen atom of bench-stable electrophilic aminating agents. Practical single and double polarity reversal (i.e., umpolung) of the nitrogen atom is achieved using sterically and electronically tunable ketomalonate-derived imines and oximes. Overall, this novel approach represents an operationally simple, scalable, and environmentally friendly alternative to transition-metal-catalyzed C-N cross-coupling methods that are currently used to access structurally diverse secondary amines.
