108191-12-4Relevant academic research and scientific papers
Copper-Catalyzed C(sp3)?H Amidation: Sterically Driven Primary and Secondary C?H Site-Selectivity
Bakhoda, Abolghasem (Gus),Jiang, Quan,Badiei, Yosra M.,Bertke, Jeffery A.,Cundari, Thomas R.,Warren, Timothy H.
supporting information, p. 3421 - 3425 (2019/02/14)
Undirected C(sp3)?H functionalization reactions often follow site-selectivity patterns that mirror the corresponding C?H bond dissociation energies (BDEs). This often results in the functionalization of weaker tertiary C?H bonds in the presence of stronger secondary and primary bonds. An important, contemporary challenge is the development of catalyst systems capable of selectively functionalizing stronger primary and secondary C?H bonds over tertiary and benzylic C?H sites. Herein, we report a Cu catalyst that exhibits a high degree of primary and secondary over tertiary C?H bond selectivity in the amidation of linear and cyclic hydrocarbons with aroyl azides ArC(O)N3. Mechanistic and DFT studies indicate that C?H amidation involves H-atom abstraction from R-H substrates by nitrene intermediates [Cu](κ2-N,O-NC(O)Ar) to provide carbon-based radicals R. and copper(II)amide intermediates [CuII]-NHC(O)Ar that subsequently capture radicals R. to form products R-NHC(O)Ar. These studies reveal important catalyst features required to achieve primary and secondary C?H amidation selectivity in the absence of directing groups.
Synthesis and Anticonvulsant Activity of Analogues of 4-Amino-N-(1-phenylethyl)benzamide
Clark, C. Randall,Davenport, Timothy W.
, p. 1214 - 1218 (2007/10/02)
A group of amides and amines related to 4-amino-N-(1-phenylethyl)benzamide, 1, were prepared in a study on the relationship of structure to anticonvulsant activity in this compound. Acylation and alkylation of the amino group of 1 resulted in almost total loss of anticonvulsant activity. Insertion of a methylene between the 4-amino group and the aromatic ring of 1 produced a slight increase in anticonvulsant potency and a significant increase in toxicity. Hydride reduction of the amide carbonyl in 1 also yielded compounds having a slightly lower ED50 against convulsions induced by electroshock and a much lower TD50 in the rotorod assay. Modification of the 1-phenylethyl group of 1 also decreased anticonvulsant potency.
