Nucleophilic Nitration of Arynes by Sodium Nitrite and its Multicomponent Reaction Leading to Double-Functionalized Arenes

Abstract

An unusual nucleophilic nitration of arynes by NaNO2 in the presence of water has been developed, and the concept was further demonstrated to accomplish a double functionalization of arynes using a multicomponent reaction protocol to synthesize pharmaceutically important (2-nitrophenyl)methanol derivatives. Such substitution ortho to -NO2 is difficult by other means. The reaction conditions are mild and avoid the use of strong acids, expensive transition metal catalysts, and additives.

Recent Advances in Retained and Dehydrogenative Dual Functionalization Chemistry

“…Singh and co-workers recently reported a Rh(II)-catalyzed annulative coupling reaction of β-ketothioamides (29) with αdiazo compounds (30) to obtain corresponding thiazolidinones (31) (Scheme 9). [13] The annulative coupling reaction proceeds through the generation of rhodium carbenoid species (29-A) from Rh(OAc) 2 and 30 via the extrusion of nitrogen.…”

“…Based on the above reaction mechanism, a three‐component coupling of 2‐(trimethylsilyl)aryl triflates ( 67 ) with aminosilanes ( 68 ) and aldehydes or aldimines ( 69 ) to provide 2‐aminobenzhydrols or 2‐aminobenzhydrylamines ( 70 ) by Yoshida and co‐workers (Scheme 22a), [29] and a three‐component coupling of 2‐(trimethylsilyl)aryl triflates ( 71 ) with sodium nitrite and aldehydes ( 72 ) to provide (2‐nitrophenyl)methanol derivatives ( 73 ) by Mhaske and co‐worker (Scheme 22b) [30] were reported.…”

Applications of Sodium Nitrite in Organic Synthesis

“…Dhokale and Mhaske reported the synthesis of nitroaromatics 49 via an unusual NaNO 2 ‐mediated nucleophilic nitration of arynes in the presence of water as the proton source (Scheme ) . The arynes in turn were generated from 48 using CsF as the fluoride source.…”

“…Dhokale and Mhaske reported the synthesis of nitroaromatics 49 via an unusual NaNO 2 -mediated nucleophilic nitration of arynes in the presence of water as the proton source (Scheme 42). [37] The arynes in turn were generated from 48 using CsF as the fluoride source. Such nitration was compatible with the alkyl-substituted aryne precursors as well as unsubstituted 48 but failed to give pure products with halo substituted arynes.…”

Diastereoselective Synthesis of Symmetrical and Unsymmetrical Tetrahydropyridines Catalyzed by Bi(III) Immobilized on Triazine Dendrimer Stabilized Magnetic Nanoparticles

“…One-pot multicomponent reactions (MCRs) are remarkably useful for the synthesis of a diverse range of heterocyclic systems, with advantages of selectivity and atom economy . A variety of catalysts have been used for the synthesis of THP derivatives from aryl aldehydes, aryl amines, and β-ketoesters, including cerium ammonium nitrate (CAN), InCl 3 , Bi­(NO 3 ) 3 ·5H 2 O, l -proline/TFA, BF 3 ·SiO 2 , and molecular iodine .…”