An electrochemical amidation of benzoyl hydrazine/ carbazate and primary/secondary amine as coupling partners via concomitant cleavage and formation of C(sp 2 )−N bonds has been achieved. This methodology proceeds under metal-free and exogenous oxidant-free conditions producing N 2 and H 2 as byproducts. Mechanistic studies reveal the in situ generations of both acyl and N-centered radicals from benzoyl hydrazines and amines. The utility of this protocol is demonstrated through a largescale, and synthesis of bezafibrate, a hyperlipidemic drug.
The nitrile or cyano (-CN) group is one of the most appreciated and effective functional groups in organic synthesis having a polar unsaturated C-N triple bond. Despite sufficient stability and...
In the arena of functional group-oriented organic synthesis, nitrile or cyano functionality is of immense importance. The presence of nucleophilic N-atom, π-coordinating ability of the triple bond, and electrophilic C-center imparts unique and interesting reactivities. Owing to the ability of the nitrile to transform into various other functional groups or intermediates, the chemistry is very rich and diverse. In particular, the involvement of nitrile in numerous organic reactions such as inter-or intramolecular alkyne insertion, [2 + 2 + 2] cycloaddition with alkynes, [3 + 2] cycloaddition with azides, [4 + 2] cycloaddition with dienes allow the synthesis of many important carbo-and heterocycles. Furthermore, the nitrile serves as a directing group in many CÀ H bond functionalization reactions to introduce diverse functionalities and participate as a radical acceptor in radical cascade strategies to obtain a large variety of functional molecules. This review mainly focuses on the reactivity and diverse synthetic application of the nitrile including CÀ H bond functionalization, alkyne insertion, cycloaddition, and thermal or photochemical cascade strategy. The objective of the current review aims at bringing out the striking collection of various nitrile-triggered organic transformations.
A Pd(II)-catalyzed synthesis of furopyridines
has been developed
from β-ketodinitriles and alkynes via an unusual N–H/C
annulation. The participation of both the nitrile groups and the concurrent
construction of furan and pyridine rings through the formation of
C–C, CC, C–O, C–N, and CN bonds
are the important features. The synthetic applicability is further
demonstrated through a series of postsynthetic alterations.
A solvent (2,2,2-trifluoroethanol (TFE) vs ethyl alcohol
(EtOH))
switched synthesis of quinolines and pyridines is illustrated from
(E)-2-(1,3-diphenylallylidene)malononitriles via
a Pd(II)-catalyzed photochemical process. The active catalyst [L2Pd(0)] generated serves as an exogenous photosensitizer. The
process offers predominantly Z-alkenylated quinolines
and pyridines in TFE and EtOH, respectively. Furthermore, large-scale
synthesis and a few interesting post-synthetic modifications have
been demonstrated.
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