Oxidative coupling
of benzylamines and alcohols with methyl substituted N-heteroarenes such as quinolines and quinoxalines has been
achieved using chloride, a sea abundant anion as the catalyst for
practical synthesis of a wide range of E-disubstituted
olefins in aqueous medium. Detailed mechanistic studies and control
experiments were carried out to deduce the reaction mechanism which
indicated that in situ formed ClO2
– is the active form of the catalyst. We have successfully
carried out a 1 g scale reaction using this methodology, and five
pharmaceutically relevant conjugated olefins were also synthesized
by this method in moderate to good yields.
Herein, we report a simple, efficient, and sustainable method for the synthesis of α‐alkylated ketones and quinolines using a hydrogen‐borrowing strategy, which has emerged as a greener alternative in organic transformation reactions. Synthesis of a range of α‐alkylated ketones and quinoline derivatives was achieved by using the water‐soluble [Ru(8‐AQ)Cl(p‐cym.)]+Cl− [Ru]‐1 (AQ=aminoquinoline) catalyst with water as the reaction medium. By adopting this strategy, we have synthesized α‐alkylated ketones and quinolines using ketones or secondary alcohols as starting materials and the primary alcohol as a green and naturally abundant alkylating agent.
Herein, we report a new method for the synthesis of aminodiborane (µ-NH2B2H5), by the reaction of NH3BH3 and elemental iodine (I2). The in situ generated aminodiborane is used as a...
Herein, we report a palladium‐catalyzed ‘on‐water’ methodology for the synthesis of biaryl and m‐teraryl derivatives of aryl carboxamides by selective mono and bis C−H bond functionalization. 8‐aminoquinoline and 2‐thiomethylaniline were used as directing groups for C−H bond functionalization of aryl carboxamides with various aryl and alkyl iodides using 3.0–4.0 mol% of Pd(OAc)2 as catalyst and water as the solvent resulting in 45–97% isolated yields of the mono and bis C−H bond functionalized products. Using an 8‐aminoquinoline carboxamide core, C−H bond functionalization of indole‐3‐carboxylic acid and a late‐stage functionalization of aspirin molecule have also been carried out. Reactions of benzyl/naphthyl picolinamides with aryl iodides gave 60–96% yield of the arylated products using the picolinamide directing group. Moreover, the insoluble nature of products in an aqueous medium enabled us to explore the reusability of the solvent, i. e., water and the catalyst. Control experiments and structural studies were carried out which confirmed the in situ formation of unique palladacycles during the reaction. Removal of the directing groups has been carried out to convert the functionalized products into amines and fluorenone compounds useful in industrial and pharmaceutical applications.
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