13429-10-2Relevant articles and documents
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Proskouriakoff,Titherington
, p. 3978,3982 (1930)
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Cp?Rh(III)/Bicyclic Olefin Cocatalyzed C-H Bond Amidation by Intramolecular Amide Transfer
Wang, Xiaoming,Gensch, Tobias,Lerchen, Andreas,Daniliuc, Constantin G.,Glorius, Frank
, p. 6506 - 6512 (2017/05/17)
A bicyclic olefin was discovered as a cocatalyst in a Cp?Rh(III)-catalyzed C-H bond amidation proceeding by an intramolecular amide transfer in N-phenoxyacetamide derivatives. Combining experimental and theoretical studies, we propose that the olefin promotes a Rh(III) intermediate to undergo oxidative addition into the O-N bond to form a Rh(V) nitrenoid species and subsequently direct the nitrenoid to add to the ortho position. The amide directing group plays a dual role as a cleavable coordinating moiety as well as an essential coupling partner for the C-H amidation. This methodology was successfully applied to the late-stage diversification of natural products and a marketed drug under mild conditions.
Divergent reactivities of o-haloanilides with CuO nanoparticles in water: A green synthesis of benzoxazoles and o-hydroxyanilides
Khatun, Nilufa,Guin, Srimanta,Rout, Saroj Kumar,Patel, Bhisma K.
, p. 10770 - 10778 (2014/03/21)
In the present study, three divergent reaction paths emerged when o-haloanilides were subjected to CuO nanoparticles in water. o-Halo (I, Br) phenylbenzamides in the presence of CuO nanoparticles and Cs2CO 3 in water at 100 °C provided o-hydroxyphenyl benzamides as the major product. However, a complete change in selectivity was observed in the presence of an organic base/ligand (TMEDA), giving 2-arylbenzoxazole as the exclusive product. The above selectivities were not clearly distinct when the corresponding alkylamides were treated either in the presence or absence of the ligand. A number of o-halophenyl alkylamides provided either exclusively o-dehalogenated products or a mixture of o-dehalogenated and o-hydroxylated products, but none gave 2-alkylbenzoxazoles. In addition to the above selectivities, the use of an environmentally friendly solvent (water) and base, and the recyclability of the catalyst make this procedure a benign alternative to the existing methods for the synthesis of these molecules, viz. o-hydroxybenzamides and o-arylbenzoxazoles.