Palladium-catalyzed cross-coupling of five-membered heterocyclic silanolates.

The Journal of Organic Chemistry
Scott E DenmarkChristopher S Regens

Abstract

The preparation of pi-rich 2-aryl heterocycles by palladium-catalyzed cross-coupling of sodium heteroarylsilanolates with aryl iodides, bromides, and chlorides is described. The cross-coupling process was developed through extensive optimization of the following key variables: (1) identification of stable, isolable alkali metal silanolates, (2) identification of conditions for preformation and isolation of silanolate salts, (3) judicious choice in the palladium catalyst/ligand combination, and (4) selection of the protecting group on the nitrogen of indole. It was found that the alkali metal silanolates, either isolated or formed in situ, offered a significant rate enhancement and broader substrate scope over the use of silanols activated by Brønsted bases such as NaOt-Bu. In addition, the optimized conditions for the cross-coupling of 2-indolylsilanolates were readily applied to the cross-coupling of 2-pyrrolyl-, 2-furyl-, and 2-thienylsilanolates.

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Citations

May 12, 2011·Chemical Reviews·Sandro Cacchi, Giancarlo Fabrizi
Feb 10, 2009·Journal of the American Chemical Society·Scott E DenmarkJoseck M Muhuhi
Oct 20, 2015·Organic Process Research & Development·Scott E Denmark, Andrea Ambrosi
May 10, 2013·The Journal of Organic Chemistry·Kai ChengChenze Qi
Apr 25, 2014·The Journal of Organic Chemistry·Feng Zhu, Zhong-Xia Wang
Oct 5, 2016·The Journal of Organic Chemistry·Stefano CrespiMaurizio Fagnoni
Nov 4, 2016·Organic Letters·Patrick R MelvinMichael J Williams
Jun 16, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·A M PredaM Mehring
Apr 7, 2016·Chemical Society Reviews·Nilay Hazari, Damian P Hruszkewycz
Jan 31, 2012·Angewandte Chemie·Graham R DickMartin D Burke
Mar 25, 2010·Angewandte Chemie·Scott E Denmark, Jack H-C Liu
Dec 1, 2010·Israel Journal of Chemistry·Scott E Denmark, Jack H-C Liu
Nov 4, 2011·Chemical Society Reviews·Hannah F SoreDavid R Spring
Mar 26, 2014·Chemistry : a European Journal·Jianguo WuMichael K Takase
Aug 25, 2010·Chemical Communications : Chem Comm·Shi TangTamejiro Hiyama
Jul 15, 2011·Chemical Society Reviews·Yoshiaki Nakao, Tamejiro Hiyama
Oct 17, 2009·The Journal of Organic Chemistry·Jean-Hugues MirebeauFranck Le Bideau
Oct 29, 2009·The Journal of Organic Chemistry·Aaron D FinkeJeffrey S Moore
Nov 15, 2008·The Journal of Organic Chemistry·Haruhiko Fuwa, Makoto Sasaki
May 15, 2010·Organic Letters·Graham R DickMartin D Burke

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