Methods for the synthesis and functionalization of amines are intrinsically important to a variety of chemical applications. We present a general carbon-hydrogen bond activation process that combines readily available aliphatic amines and the feedstock gas carbon monoxide to form synthetically versatile value-added amide products. The operationally straightforward palladium-catalyzed process exploits a distinct reaction pathway, wherein a sterically hindered carboxylate ligand orchestrates an amine attack on a palladium anhydride to transform aliphatic amines into β-lactams. The reaction is successful with a wide range of secondary amines and can be used as a late-stage functionalization tactic to deliver advanced, highly functionalized amine products of utility for pharmaceutical research and other areas.

The selective C–H carbonylation of methylene bonds, in the presence of traditionally more reactive methyl C–H and C(sp2)–H bonds, in α-tertiary amines is reported.

. (2015) Synthesis of cyclopropyl-substituted furans by Brønsted acid promoted cascade reactions.

. (2015) Synthesis of cyclopropyl-substituted furans by Brønsted acid promoted cascade reactions.

No abstract

Synthesis of Cyclopropyl-Substituted Furans by Broensted Acid Promoted CascadeReactions. -A high-yielding, diastereoselective intramolecular reaction cascade reaction is developed creating three new bonds in a single step, thus providing 2,3,5-substituted furans bearing a ring fused cyclopropyl substituent. Due to the instability of some of the required ynenone substrates an in-situ-preparation of the latter starting from 2-alkynals and acetylacetone is examined. The reaction is extended to a substrate bearing a pendant alkyne which cyclices to form a tricyclic acetal structure. -(CLARK*, J. S.; ROMITI, F.; HOGG, K. F.; HAMID, M. H. S. A.; RICHTER, S. C.; BOYER, A.; REDMAN, J. C.; FARRUGIA, L. J.; Angew. Chem., Int. Ed. 54 (2015) 19, 5744-5747, http://dx.doi.org/10.1002/anie.201500625 ; WestCHEM, Sch.