Publication Date:
2009-12-08
Description:
The Mizoroki-Heck reaction, which couples aryl halides with olefins, has been widely used to stitch together the carbogenic cores of numerous complex organic molecules. Given that the position-selective introduction of a halide onto an arene is not always straightforward, direct olefination of aryl carbon-hydrogen (C-H) bonds would obviate the inefficiencies associated with generating halide precursors or their equivalents. However, methods for carrying out such a reaction have suffered from narrow substrate scope and low positional selectivity. We report an operationally simple, atom-economical, carboxylate-directed Pd(II)-catalyzed C-H olefination reaction with phenylacetic acid and 3-phenylpropionic acid substrates, using oxygen at atmospheric pressure as the oxidant. The positional selectivity can be tuned by introducing amino acid derivatives as ligands. We demonstrate the versatility of the method through direct elaboration of commercial drug scaffolds and efficient syntheses of 2-tetralone and naphthoic acid natural product cores.〈br /〉〈br /〉〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2879878/" target="_blank"〉〈img src="https://static.pubmed.gov/portal/portal3rc.fcgi/4089621/img/3977009" border="0"〉〈/a〉 〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2879878/" target="_blank"〉This paper as free author manuscript - peer-reviewed and accepted for publication〈/a〉〈br /〉〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Wang, Dong-Hui -- Engle, Keary M -- Shi, Bing-Feng -- Yu, Jin-Quan -- 1 R01 GM084019-02/GM/NIGMS NIH HHS/ -- R01 GM084019/GM/NIGMS NIH HHS/ -- R01 GM084019-02/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2010 Jan 15;327(5963):315-9. doi: 10.1126/science.1182512. Epub 2009 Nov 26.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19965380" target="_blank"〉PubMed〈/a〉
Keywords:
Alkenes/*chemistry
;
Amino Acids/chemistry
;
Carbon/*chemistry
;
Carboxylic Acids/*chemical synthesis/chemistry
;
Catalysis
;
Hydrogen/*chemistry
;
Ligands
;
Molecular Structure
;
Naphthalenes/*chemical synthesis/chemistry
;
Oxidants/chemistry
;
Oxygen/chemistry
;
Palladium/chemistry
;
Phenylacetates/chemistry
;
Phenylpropionates/chemistry
;
Physicochemical Processes
;
Tetralones/*chemical synthesis
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
,
Chemistry and Pharmacology
,
Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
Permalink