MoOPH(Redirected from MoOPH oxidation)
MoOPH, also known as oxodiperoxymolybdenum(pyridine)-(hexamethylphosphoric triamide), is a reagent used in organic synthesis. It contains a molybdenum(VI) center with multiple oxygen ligands, coordinated with pyridine and HMPA ligands. It is an electrophilic source of oxygen that reacts with enolates and related structures, and thus can be used for alpha-hydroxylation of carbonyl-containing compounds. Other reagents used for alpha-hydroxylation via enol or enolate structures include Davis oxaziridine, oxygen, and various peroxyacids (see Rubottom oxidation). This reagent was first utilized by Edwin Vedejs as an efficient alpha-hydroxylating agent in 1974 and an effective preparative procedure was later published in 1978.
|Molar mass||434.25 g·mol−1|
|Melting point||103–105 °C (217–221 °F; 376–378 K) (dec)|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
In the case of sulfones, alpha-hydroxylation leads directly to the ketone or aldehyde.
Common byproducts of the alpha-hydroxylation tend to inclue overoxidation to the corresponding dicarbonyl or intermolecular aldol reaction of the starting material. Procedures to prevent side reactions include the inverse addition of the enolate to MoOPH or careful control of the temperature (-78 to -20 °C). Notable miscellaneous reactions include MoOPH’s ability to oxidize alkylboranes directly to the alcohol with net stereo-retention.
MoOPH has also been shown to oxidize N-trimethylsilyl amides directly to the hydroxamic acid.
- Edwin Vedejs (April 15, 2001). "Oxodiperoxymolybdenum(pyridine)(hexamethylphosphoric triamide)". e-EROS Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.ro022.
- "HYDROXYLATION OF ENOLATES WITH OXODIPEROXYMOLYBDENUM(PYRIDINE)(HEXAMETHYLPHOSPHORIC TRIAMIDE), MoO5·Py·HMPA(MoOPH): 3-HYDROXY-1,7,7-TRIMETHYLBICYCLO[2.2.1]HEPTAN-2-ONE". Organic Syntheses. 64: 127. 1986. doi:10.15227/orgsyn.064.0127.
- Vedejs, E.; Engler, D. A.; Telschow, J. E. (1978-01-01). "Transition-metal peroxide reactions. Synthesis of .alpha.-hydroxycarbonyl compounds from enolates". The Journal of Organic Chemistry. 43 (2): 188–196. doi:10.1021/jo00396a002. ISSN 0022-3263.
- Yuan, Changxia; Jin, Yehua; Wilde, Nathan C.; Baran, Phil S. (2016-07-11). "Short, Enantioselective Total Synthesis of Highly Oxidized Taxanes". Angewandte Chemie International Edition. 55 (29): 8280–8284. doi:10.1002/anie.201602235. ISSN 1521-3773. PMC . PMID 27240325.
- Hanessian, Stephen; Cooke, Nigel G.; DeHoff, Brad; Sakito, Yoji (1990-06-01). "The total synthesis of (+)-ionomycin". Journal of the American Chemical Society. 112 (13): 5276–5290. doi:10.1021/ja00169a041. ISSN 0002-7863.
- Morizawa, Yoshitomi; Yasuda, Arata; Uchida, Keiichi. "Trifluoromethyl group induced highly stereoselective synthesis of α-hydroxy carbonyl compounds". Tetrahedron Letters. 27 (16): 1833–1836. doi:10.1016/s0040-4039(00)84388-9.
- Vedejs, E.; Telschow, J. E. (1976-02-20). "Synthesis of cyanohydrins from cyanides. Transition metal peroxide reactions". The Journal of Organic Chemistry. 41 (4): 740–741. doi:10.1021/jo00866a048. ISSN 0022-3263.
- Little, R.Daniel; Myong, Sun Ok. "Oxidative desulfonylation. Phenyl vinyl sulfone as a ketene synthetic equivalent". Tetrahedron Letters. 21 (35): 3339–3342. doi:10.1016/s0040-4039(00)78683-7.
- Midland, M. Mark; Preston, Scott B. (1980-10-01). "Stereochemistry of molybdenum peroxide oxidation of organoboranes". The Journal of Organic Chemistry. 45 (22): 4514–4515. doi:10.1021/jo01310a054. ISSN 0022-3263.
- Matlin, S. A.; Sammes, P. G. (1972-01-01). "A new method for the preparation of hydroxamic acids from secondary amides". Journal of the Chemical Society, Chemical Communications (22). doi:10.1039/c39720001222. ISSN 0022-4936.