By Kevin H. Shaughnessy, Engelbert Ciganek, Rebecca B. DeVasher, Scott E. Denmark
The metal-catalyzed amination of aryl and alkenyl electrophiles has constructed right into a generic technique for the synthesis of common items, lively pharmaceutical components, agricultural chemical compounds, and fabrics for molecular electronics. Copper catalysts advertise the coupling of quite a lot of nitrogen nucleophiles, together with amines, amides, and heteroaromatic nitrogen compounds with aryl and alkenyl halides. The reactivity profile of copper catalysts is complementary to that of palladium catalysts in lots of situations. Copper catalysts are powerful with much less nucleophilic nitrogen nucleophiles, similar to amides and azoles, while palladium catalysts are more beneficial with extra nucleophilic amine nucleophiles. Copper is an enticing substitute to palladium because of its considerably lower price. additionally, excessive job palladium catalysts require dear and sometimes air-sensitive ligands, while the trendy copper structures use rather solid and cheap diamine or amino acid ligands. Copper-catalyzed C?N coupling reactions are tolerant of a variety of practical teams and feature been utilized to the synthesis of various complicated common items. major paintings has additionally been performed to appreciate the mechanism of those reactions. present mechanistic realizing of those methodologies is roofed during this monograph.
The contents of the ebook are taken from the great assessment of the subject within the natural Reactions sequence. optimum experimental stipulations for the amination of aryl and alkenyl halides with all periods of nitrogen nucleophiles are awarded. particular experimental tactics from the literature are supplied for the main periods of copper-catalyzed C?N coupling reactions. A tabular survey of all examples of Cu-catalyzed arylation and alkenylation of nitrogen nucleophiles is gifted in 35 tables equipped by way of nitrogen nucleophile and electrophilic coupling partner.
The literature is roofed via December 2015 and offers three hundred contemporary citations to complement the 680 citations of the unique hardbound bankruptcy. those newest literature references were accrued in separate sections in response to the series of the tables within the tabular survey part. In all of the sections, the person citations were prepared in alphabetic order of the writer names.
Copper-Catalyzed Amination of Aryl and Alkenyl Electrophiles is meant to supply natural chemists with an obtainable, yet exact, creation to this crucial classification of adjustments
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Additional resources for Copper-catalyzed amination of aryl and alkenyl electrophiles
No successful examples of tetrazole arylation have been reported. Azole N-arylation reactions are highly tolerant of substitution on the azole ring, but do show similar steric and electronic effects to other nitrogen nucleophiles. Substitution next to the nucleophilic nitrogen can reduce the rate of coupling, thus requiring higher temperatures and/or catalyst loadings to achieve high yields. 82 Increasing the reaction temperature to 110∘ and changing the ligand to a tetradentate bis(imine) increases the yield to 75% (Scheme 49), which is still lower than that observed with unhindered pyrazoles.
0 MeO OMe N OH ligand A N N ligand B Scheme 54 used model substrate. 139 – 143 Br + H2N N H Boc CuI (10 mol%), 4-HOPro (20 mol%) NH2 N Boc Cs2CO3, DMSO, 80°, 24 h (90%) Scheme 55 EtO2C O I + H2N N H CuI (10 mol%) Ph Cs2CO3, DMF, 80°, 21 h EtO2C H N O N H Ph (63%) Scheme 56 NH I + Br HN Ph CuI (15 mol %), DMEDA (30 mol %) Cs2CO3, DMA, 100°, 16 h N N Ph (57%) Scheme 57 N-Arylation of carbamates, ureas, and guanidines has been reported for a number of catalyst systems. Carbamates typically show comparable reactivity to structurally similar amides.
82 Increasing the reaction temperature to 110∘ and changing the ligand to a tetradentate bis(imine) increases the yield to 75% (Scheme 49), which is still lower than that observed with unhindered pyrazoles. 128 Cu2O (5 mol %), ligand (20 mol %) I + N N H Cs2CO3, DMF, 110°, 24 h N N N (75%) N N N ligand Scheme 49 Arylation of azoles is generally highly selective for N-arylation over C-arylation. For non-symmetrical azoles with multiple nitrogen centers, mixtures of products are often obtained, since each nitrogen atom can share the negative charge due to resonance delocalization.