noyori reduction (asymmetric hydrogenation)...2012/04/30 · ryoji noyori •born in 1938 in kobe,...
TRANSCRIPT
Noyori Reduction
(Asymmetric Hydrogenation)
Daniel Tao
Overman Group Meeting
4/30/12
Ryoji Noyori
•Born in 1938 in Kobe, Japan
•Received B.S. and Ph.D. from Kyoto
University
•Postdoctoral work with E.J. Corey before
returning to Nagoya University in Japan •Shared the 2001 Nobel Prize with K.B. Sharpless and W.S. Knowles
www.nobelprize.org/nobel_prizes/chemistry/laureates/2001/noyori-photo.html
Initial Work in the 1980’s
Noyori, R. et al. J. Am. Chem. Soc. 1980, 102, 7932–7934.
Noyori, R. et al. J. Am. Chem. Soc. 1984, 106, 5208–5217.
Switching to Ru(II) Catalyst
Noyori, R.; Ohta, M.; Hsiao, Y.; Kitamura, M. J. Am. Chem. Soc., 1986, 108, 7117–7119.
•23 °C for 2–3 days
•4 atm H2
•Yields almost quantitative •ee’s >95%
Asymmetric Reduction of Ketones
Noyori, R. et al. J. Am. Chem. Soc. 1987, 109, 5856–5858.
Noyori, R. et al. J. Am. Chem. Soc. 1988, 110, 629–631.
Beck, G.; Jendralla, H.; Kesseler, K. Synthesis 1995, 1014–1018.
Catalytic Cycle
Application in Dynamic Kinetic Resolution
Noyori, R. et al. J. Am. Chem. Soc. 1989, 111, 9134–9135.
Proposed Transition State
Dynamic Resolution in Synthesis
Noyori Reduction in Synthesis
Taber, D.F.; Wang, Y. J. Am. Chem. Soc. 1997, 119, 22–26.
Rychnovsky, S.D.; Hoye, R.C. J. Am. Chem. Soc. 1994, 116, 1753–1765.
Other Ligands for Noyori Reduction
Burk, M.J.; Harper, T.G.; Kalberg, C.S. J. Am. Chem. Soc. 1995, 117, 4423–4424.
Pye, P.J.; Rossen, K.; Reamer, R.A.; Volante, R.P.; Reider, P.J. Tetrahedron Lett. 1998, 39, 4441–4444.
Other Ligands for Noyori Reduction
Noyori, R.; Ohkuma, T. Pure Appl. Chem. 2001, 73, 227–232.
Other Ligands for Noyori Reduction
Noyori, R.; Ohkuma, T. Pure Appl. Chem. 2001, 73, 227–232.
Summary
•The Noyori reduction is asymmetric with
typically high enantioselectivity
•Using a Ru-based catalyst with a variety of
ligands, the transition state may be 4-
centered or 6-centered
•The substrate scope is large, based mainly
on proximity to a heteroatom (vinylic to
homoallylic)