Reações de oxidação assimétrica

Reações de oxidação assimétrica
Química Orgânica III
Profa. Arlene G. Corrêa
DQ-UFSCar
Sharpless: Oxidações catalíticas
1980: obteve um
método prático para a
oxidação catalítica
assimétrica de álcoois
de alila em epóxidos
quirais
(R)-Glicidol usado na indústria farmacêutica para a
obtenção de agentes β-blockers que são usados em
cardiopatias
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2001/advanced-chemistryprize2001.pdf
Sharpless Epoxidation
http://www.masterorganicchemistry.com/reaction-guide/sharpless-epoxidation/
http://www.masterorganicchemistry.com/reaction-guide/sharpless-epoxidation/
Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc.
1980, 102, 5974–5976.
http://pt.slideshare.net/dragnerkar/dynamic-stereochemistry-stereoselectivity
Jacobsen Epoxidation
http://www.namereactions.org/jacobsen-katsuki-epoxidation/
http://www.organic-chemistry.org/namedreactions/jacobsen-katsuki-epoxidation.shtm
Wei Zhang, Jennifer L. Loebach, Scott R. Wilson, and Eric N. Jacobsen J. Am. Chem. Soc.; 1990; 112(7) pp 2801 – 2803.
http://medlibrary.org/medwiki/Jacobsen_epoxidation
http://www.shasun.com/?page_id=1145
Sharpless Dihydroxylation
http://www.chem-station.com/en/reactions-2/2014/06/sharpless-asymmetric-dihydroxylation-sharpless-ad.html
Sharpless Dihydroxylation Mechanism
DelMonte, A. J.; Haller, J.; Houk, K. N.; Sharpless, K. B.; Singleton, D. A.; Strassner, T.; Thomas, A. A. J. Am. Chem. Soc. 119: 9907 (1997).
N-methylmorpholine N-oxide as co-oxidant
Enantioselectivity depends on the alkene
concentration: very slow addition is
required for better ee
http://www.chem-station.com/en/reactions-2/2014/06/sharplessasymmetric-dihydroxylation-sharpless-ad.html
Regio- and stereoselectivity depends on the alkene
Xu, D.; Crispino, G. A.; Sharpless, K. B. J. Am. Chem. Soc. 114 (19): 7570–7571(1992).
Corey, E. J.; Guzman-Perez, Angel; Noe, Mark C. J. Am. Chem. Soc. 117 (44): 10805–10816 (1995).