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Palladium catalyzed transformations of monoterpenes: stereoselective deuteriation and oxidative dimerization of camphene
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UNSPECIFIED. (2004) Palladium catalyzed transformations of monoterpenes: stereoselective deuteriation and oxidative dimerization of camphene. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 689 (2). pp. 302-308. ISSN 0022-328X
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Official URL: http://dx.doi.org/10.1016/j.jorganchem.2003.10.016
Abstract
Camphene undergoes a highly regio and stereoselective palladium catalyzed deuteriation in deuteriated acetic acid solutions of Pd(OAc)(2). NMR reveals that an outward oriented vinylic hydrogen is selectively exchanged for H-2, resulting in 90% camphene-d(1) (ca. 100% stereoselectivity) and 10% camphene-d(2) at 75% conversion of camphene (6 h, 25 degreesC). Neither pi-allyl nor pi-olefin palladium complexes are formed in detectable concentrations during the reaction, whereas palladium hydride (singlet at -6.86 ppm) and palladium deuteride (singlet at -6.78 ppm) intermediates have been detected by H-1 and H-2 NMR, respectively. At higher temperature, oxidative coupling of camphene readily occurs giving the (E, E)-diene, i.e., bis(3,3-dimethyl-2-norbornylidene)ethane, which formally originates by abstracting the outward oriented vinylic hydrogens and coupling the resulting fragments of two camphene molecules. The reaction is catalytic at palladium in the Pd(OAc)(2)-LiNO3(cat)-O-2 and Pd(OAc)(2)-benzoquinone systems. Similar mechanisms for the deuteriation and oxidative coupling of camphene are proposed, which involve the formation of sigma-vinyl palladium hydride intermediates. No deuteriation neither oxidative coupling of limonene, myrcene and beta-pinene were observed under the same conditions. (C) 2003 Elsevier B.V. All rights reserved.
| Item Type: | Journal Article |
|---|---|
| Subjects: | Q Science > QD Chemistry |
| Journal or Publication Title: | JOURNAL OF ORGANOMETALLIC CHEMISTRY |
| Publisher: | ELSEVIER SCIENCE SA |
| ISSN: | 0022-328X |
| Date: | 15 January 2004 |
| Volume: | 689 |
| Number: | 2 |
| Number of Pages: | 7 |
| Page Range: | pp. 302-308 |
| Identification Number: | 10.1016/j.jorganchem.2003.10.016 |
| Publication Status: | Published |
| URI: | http://wrap.warwick.ac.uk/id/eprint/8825 |
Data sourced from Thomson Reuters' Web of Knowledge
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