skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Palladium-catalyzed Br/D exchange of arenes: Selective deuterium incorporation with versatile functional group tolerance and high efficiency

Abstract

There is a facile method for introducing one or more deuterium atoms onto an aromatic nucleus via Br/D exchange with high functional group tolerance and high incorporation efficiency is disclosed. Deuterium-labeled aryl chlorides and aryl borates which could be used as substrates in cross-coupling reactions to construct more complicated deuterium-labeled compounds can also be synthesized by this method.

Authors:
 [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1210145
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Organic Chemistry Frontiers (Online)
Additional Journal Information:
Journal Name: Organic Chemistry Frontiers (Online); Journal Volume: 2; Journal Issue: 9; Journal ID: ISSN 2052-4129
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Honghai -Hai, Bonnesen, Peter V., and Hong, Kunlun. Palladium-catalyzed Br/D exchange of arenes: Selective deuterium incorporation with versatile functional group tolerance and high efficiency. United States: N. p., 2015. Web. doi:10.1039/C5QO00181A.
Zhang, Honghai -Hai, Bonnesen, Peter V., & Hong, Kunlun. Palladium-catalyzed Br/D exchange of arenes: Selective deuterium incorporation with versatile functional group tolerance and high efficiency. United States. doi:10.1039/C5QO00181A.
Zhang, Honghai -Hai, Bonnesen, Peter V., and Hong, Kunlun. Mon . "Palladium-catalyzed Br/D exchange of arenes: Selective deuterium incorporation with versatile functional group tolerance and high efficiency". United States. doi:10.1039/C5QO00181A. https://www.osti.gov/servlets/purl/1210145.
@article{osti_1210145,
title = {Palladium-catalyzed Br/D exchange of arenes: Selective deuterium incorporation with versatile functional group tolerance and high efficiency},
author = {Zhang, Honghai -Hai and Bonnesen, Peter V. and Hong, Kunlun},
abstractNote = {There is a facile method for introducing one or more deuterium atoms onto an aromatic nucleus via Br/D exchange with high functional group tolerance and high incorporation efficiency is disclosed. Deuterium-labeled aryl chlorides and aryl borates which could be used as substrates in cross-coupling reactions to construct more complicated deuterium-labeled compounds can also be synthesized by this method.},
doi = {10.1039/C5QO00181A},
journal = {Organic Chemistry Frontiers (Online)},
number = 9,
volume = 2,
place = {United States},
year = {Mon Jul 13 00:00:00 EDT 2015},
month = {Mon Jul 13 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

Save / Share:
  • Arthracene and anthraquinone can be converted to 9,9,l0,10tetradeuterio- 9,10-dihydroanthracene in the presence of excess D/sub 2/ (or D/sub 2/O), CO, and catalytic amounts of Co/sub 2/(CO)/sub 8/. Pyre ne also undergoes reduction and H- D exchange at the 4 and 5 positions; phenanthrene fails to react. When 1- octene is treated with CO and Co/sub 2/(CO)/sub 8/ in the presence of the tetradeuteriodihydroa nthracene, as a deuterium source, C/sub 9/ aldehydes, randomly substituted with deuterium, result. (auth)
  • The stereochemistry of the palladium catalyzed exchange of deuterium with the allylic hydrogens of cholest-8(14)-en-3..beta..-ol,2, has been examined in a test of the Rooney, Gault, and Kemball hypothesis that a ..pi..-allylic surface intermediate is able to react directly with molecular hydrogen. The test compound was selected from evidence that only one face of the double bond is accessible to a catalytic surface. The correlation of mass, /sup 13/C nuclear magnetic resonance, and infrared spectral data shows that no more than one hydrogen atom in each allylic methylene group is replaced (C-7 and C-15). Because the RGK mechanism would require thatmore » both hydrogens should be replaced, it cannot be operating in this system. The isomerization of cholest-7-en-3..beta..-ol to 2 is catalyzed in benzene solutions by PdCl/sub 2/(C/sub 6/H/sub 5/CN)/sub 2/ but not by HRh(PPh/sub 3/)/sub 4/, which lends support to the hypothesis that ..pi..-allylic but not ''half-hydrogenated'' intermediates are involved in the related palladium-catalyzed isomerization and exchange reactions of these steroids.« less
  • Organometallic halide perovskite solar cells (PSCs) have shown great promise as a low-cost, high-efficiency photovoltaic technology. Structural and electro-optical properties of the perovskite absorber layer are most critical to device operation characteristics. Here we present a facile fabrication of high-efficiency PSCs based on compact, large-grain, pinhole-free CH 3NH 3PbI 3-xBr x (MAPbI 3-xBr x) thin films with high reproducibility. A simple methylammonium bromide (MABr) treatment via spin-coating with a proper MABr concentration converts MAPbI 3 thin films with different initial film qualities (for example, grain size and pinholes) to high-quality MAPbI 3-xBr x thin films following an Ostwald ripening process,more » which is strongly affected by MABr concentration and is ineffective when replacing MABr with methylammonium iodide. A higher MABr concentration enhances I-Br anion exchange reaction, yielding poorer device performance. Lastly, this MABr-selective Ostwald ripening process improves cell efficiency but also enhances device stability and thus represents a simple, promising strategy for further improving PSC performance with higher reproducibility and reliability.« less