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Enantioselective Rhodium (I) Donor Carbenoid-Mediated Cascade Triggered by a Base-Free Decomposition of Arylsulfonyl Hydrazones

The reaction of diyne arylsulfonyl hydrazone substrates under rhodium(I)/BINAP catalysis gives access to sulfonated azacyclic frameworks in a highly enantioselective manner. This new cascade process considerably increases the molecular complexity by generating two C-C bonds, one C-S bond, and one C-H bond. Theoretical calculations, competitive experiments, and deuterium labeling have jointly been used to propose a mechanism that accounts for the reaction. The mechanism involves the formation of vinyl rhodium carbenoids, hydride migratory insertion, and intermolecular stereoselective nucleophilic attack. The last two steps are the key to the stereoselectivity of the process

La reaccio catalitzada per rodi(I)/BINAP de substrats contenint dos alquins i una sulfonilhidrazona permet sintetitzar compostos nitrogenats amb un grup sulfona de forma altament enantioselectiva. Aquest nou proces en cascada augmenta considerablement la complexitat molecular ja que genera dos enllacos CC, un enllac CS i un enllac CH. Sha proposat un mecanisme per al proces desenvolupat en base als resultats obtinguts mitjancant calculs DFT, experiments de competicio i marcatge amb deuteri. El mecanisme involucra la formacio dun vinilcarbenoid de rodi, una insercio migratria dhidrur i un atac nucleofilic intermolecular estereoselectiu. Els dos darrers passos son claus per a lenantioselectivitat del proces

This research was funded by the Spanish Ministry of Education and Science (MINECO) (CTQ2014-54306-P and CTQ2012-32436) and the DIUE of the Generalitat de Catalunya (2014SGR931, ICREA Academia 2014 to M.S., and FI predoctoral grant to O.T.). M.S. acknowledges funding through the European Union (EU) FEDER fund (UNGI10-4E-801)

info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/

Wiley-VCH Verlag

Manager: Ministerio de Econom铆a y Competitividad (Espanya)
Generalitat de Catalunya. Ag猫ncia de Gesti贸 d鈥橝juts Universitaris i de Recerca
Author: Torres Ant贸n, 脪scar
Parella Coll, Teodor
Sol脿 i Puig, Miquel
Roglans i Ribas, Anna
Pla i Quintana, Anna
Abstract: The reaction of diyne arylsulfonyl hydrazone substrates under rhodium(I)/BINAP catalysis gives access to sulfonated azacyclic frameworks in a highly enantioselective manner. This new cascade process considerably increases the molecular complexity by generating two C-C bonds, one C-S bond, and one C-H bond. Theoretical calculations, competitive experiments, and deuterium labeling have jointly been used to propose a mechanism that accounts for the reaction. The mechanism involves the formation of vinyl rhodium carbenoids, hydride migratory insertion, and intermolecular stereoselective nucleophilic attack. The last two steps are the key to the stereoselectivity of the process
La reaccio catalitzada per rodi(I)/BINAP de substrats contenint dos alquins i una sulfonilhidrazona permet sintetitzar compostos nitrogenats amb un grup sulfona de forma altament enantioselectiva. Aquest nou proces en cascada augmenta considerablement la complexitat molecular ja que genera dos enllacos CC, un enllac CS i un enllac CH. Sha proposat un mecanisme per al proces desenvolupat en base als resultats obtinguts mitjancant calculs DFT, experiments de competicio i marcatge amb deuteri. El mecanisme involucra la formacio dun vinilcarbenoid de rodi, una insercio migratria dhidrur i un atac nucleofilic intermolecular estereoselectiu. Els dos darrers passos son claus per a lenantioselectivitat del proces
This research was funded by the Spanish Ministry of Education and Science (MINECO) (CTQ2014-54306-P and CTQ2012-32436) and the DIUE of the Generalitat de Catalunya (2014SGR931, ICREA Academia 2014 to M.S., and FI predoctoral grant to O.T.). M.S. acknowledges funding through the European Union (EU) FEDER fund (UNGI10-4E-801)
Format: application/pdf
Document access: http://hdl.handle.net/10256/11611
Language: eng
Publisher: Wiley-VCH Verlag
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201502909
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
AGAUR/2014-2016/2014 SGR-931
Is part of: info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/
Rights: Tots els drets reservats
Subject: Compostos de nitrogen -- S铆ntesi
Nitrogen compounds -- Synthesis
Funcional de densitat, Teoria del
Density functionals
Rodi
Rhodium
Title: Enantioselective Rhodium (I) Donor Carbenoid-Mediated Cascade Triggered by a Base-Free Decomposition of Arylsulfonyl Hydrazones
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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