@article {43565, title = {Synthesis of functionalized β-keto arylthioethers by the aryne induced [2,3] Stevens rearrangement of allylthioethers}, journal = {Journal of Organic Chemistry}, volume = {82}, year = {2017}, month = {MAR}, pages = {4470{\textendash}4476}, type = {Article}, chapter = {4470{\textendash}4476}, abstract = {A mild and transition-metal-free synthesis of β-keto arylthioethers has been developed by the aryne triggered [2,3] Stevens rearrangement of allylthioethers. The key sulfur ylide intermediate for the rearrangement was formed by the S-arylation of allylthioethers with arynes generated from 2-(trimethylsilyl)aryl triflates using CsF. Later, the reaction products are converted into valuable heterocycles in two steps.}, doi = {10.1021/acs.joc.7b00479}, author = {Thangaraj, Manikandan and Gaykar, Rahul N. and Roy, Tony and Biju, Akkattu T.} } @article {45358, title = {Employing arynes for the generation of aryl anion equivalents and subsequent reaction with aldehydes}, journal = {Journal of Organic Chemistry}, volume = {83}, year = {2018}, month = {SEP}, pages = {11333-11340}, type = {Article}, abstract = {

Arynes are highly reactive intermediates, which are utilized for the electrophilic arylation of various X-H bonds (X = O, N, S etc.). Herein, a new synthetic strategy is demonstrated, where arynes are converted into aryl anion equivalents by treatment with phosphines and a base. The addition of phosphines to arynes form the phosphonium salts, which in the presence of a carbonate base generates the aryl anion equivalent. Subsequent addition of the aryl anions with aldehydes afforded the secondary alcohols.

}, doi = {10.1021/acs.joc.8b01549}, author = {Gaykar, Rahul N. and Bhunia, Anup and Biju, Akkattu T.} } @article {46166, title = {Aryne Sommelet-Hauser rearrangement}, journal = {Chemical Communications}, volume = {55}, year = {2019}, month = {MAR}, pages = {3004-3007}, type = {Article}, abstract = {

An aryne induced transition-metal-free and mild Sommelet-Hauser rearrangement of tertiary benzylamines for the synthesis of -aryl amino acid derivatives in moderate to good yields is presented. Unlike the conventional Sommelet-Hauser rearrangement of ammonium salts, the methodology developed herein requires neither harsh conditions nor strong bases. Moreover, a temperature dependent switchable selectivity for the Sommelet-Hauser and Stevens [1,2] rearrangements has been observed.

}, issn = {1359-7345}, doi = {10.1039/c9cc00629j}, author = {Roy, Tony and Gaykar, Rahul N. and Bhattacharjee, Subrata and Biju, Akkattu T.} } @article {46822, title = {Rapid synthesis of zwitterionic phosphonium benzoates by a three-component coupling involving phosphines, arynes and CO2}, journal = {Chemistry-An Asian Journal}, volume = {15}, year = {2020}, month = {JUL}, pages = {2203-2207}, type = {Article}, abstract = {

A mild and easy to perform multicomponent coupling involving phosphines, arynes generated from 2-(trimethylsilyl)aryl triflates, and CO(2)allowing the transition-metal-free synthesis of zwitterionic phosphonium benzoates has been developed. The reaction proceeds via the generation of 1 : 1 zwitterionic intermediates from phosphines and arynes followed by the interception with CO(2)to deliver the carboxylates in moderate to good yields instead of the anticipated benzooxaphosphol-3(1H)-ones.

}, keywords = {arynes, Carbon dioxide, multicomponent coupling, Phosphines, zwitterions}, issn = {1861-4728}, doi = {10.1002/asia.202000610, Early Access Date = JUN 2020}, author = {Bhattacharjee, Subrata and Raju, Anjali and Gaykar, Rahul N. and Gonnade, Rajesh G. and Roy, Tony and Biju, Akkattu T.} }