A palladium-catalyzed and norbornene-mediated
methodology has been
developed for the synthesis of chiral 2-aryl-ferroceneamides from
chiral 2-iodo-N,N-diisopropylferrocencarboxamide,
iodoarenes, and alkenes using a JohnPhos ligand and potassium carbonate
as a base in dimethylformamide at 105 °C. The developed three-component
coupling protocol allows the compatibility of electron-withdrawing
fluoro, chloro, ester, and nitro and electron-donating methyl, methoxy,
dimethoxy, benzyl ether-substituted iodo-benzenes, other iodoarenes,
such as iodo-naphthalene, heteroarenes, such as iodothiophene, and
terminating substrates, such as methyl, ethyl, tert-butyl acrylates, and substituted styrenes with 2-iodo-N,N-diisopropylferrocencarboxamide. Furthermore,
the developed three-component Catellani method proceeded with the
retention of the configuration of the planar chiral ferrocene, which
depends on the role of the participating carbon–iodine bond
in ferrocene. Consequently, the developed protocol enabled the formation
of densely substituted chiral 2-aryl ferroceneamides, exhibiting good
to excellent enantioselectivity. The conversion of an ester of the
synthesized chiral 2-aryl ferroceneamides has also been carried out
to further accommodate the easily expendable acid and alcohol functionalities.
Here, an α-selective Csp3–H bond
functionalization
of primary aliphatic alcohols with 1,4-naphthoquinones yielded Csp2
–Csp2
coupled products
driven by blue-LED light under catalyst, metal, base, and reagent-free
conditions. In this transformation, cleavage of three C–H bonds
(two sp3–C-H, one sp2–C–H,
and one O–H) and four new bonds formed, leading to fluorescent
2-acylated-1,4-naphthohydroquinones.
A one pot Cu(I)-assisted synthetic methodology has been developed for the preparation of biologically important C2-symmetric spirodiaza, benzyloxy, benzoxytelluranes from 2-bromo-N-aryl benzamides, benzyl alcohols, and benzoic acid by using tellurium...
Here, first-ever an -selective Csp3‒H bond functionalization of primary aliphatic alcohols with 1,4-naphthoquinones yield-ed Csp2‒Csp2 coupled products is reported, driven by blue-LEDs light in photo-catalyst, metal, base, reagent free conditions. In this transformation, cleavage of three C-H bonds (two sp3-C-H, one sp2-C-H, and one O-H) and four new bonds formed, leading to fluorescent 2-acylated-1,4-naphthohydroquinones.
Benzamide-derived organochalcogens (chalcogen = S, Se, and Te) have shown promising interest in biological and synthetic chemistry. Ebselen molecule derived from benzamide moiety is the most studied organoselenium. However, its heavier congener organotellurium is under-explored. Here, an efficient copper-catalyzed atom economical synthetic method has been developed to synthesize 2-phenyl-benzamide tellurenyl iodides by inserting a tellurium atom into carbon-iodine bond of 2iodobenzamides in one pot with 78-95 % yields. Further, the Lewis acidic nature of Te center and Lewis basic nature of nitrogen of the synthesized 2-Iodo-N-(quinolin-8-yl)benzamide tellurenyl iodides enabled them as pre-catalyst for the activation of epoxide with CO 2 at 1 atm for the preparation of cyclic carbonates with TOF and TON values of 1447 h À 1 and 4343, respectively, under solvent-free conditions. In addition, 2-iodo-N-(quinolin-8-yl)benzamide tellurenyl iodides have also been used as pre-catalyst for activating anilines and CO 2 to form a variety of 1,3-diaryl ureas up to 95 % yield. The mechanistic investigation for CO 2 mitigation is done by 125 Te NMR and HRMS studies. It seems that the reaction proceeds via formation of catalytically active TeÀ N heterocycle, an ebtellur intermediate which is isolated and structurally characterized.
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