Rhenium-Catalyzed Didehydroxylation of Vicinal Diols to Alkenes Using a Simple Alcohol as a ...

30 Pages·2010·1.34 MB·English

Rhenium-Catalyzed Didehydroxylation of Vicinal Diols to
Alkenes Using a Simple Alcohol as a Reducing Agent
Elena Arceo, Jonathan A. Ellman, Robert G. Bergman
J. Am. Chem. Soc. 2010, 132, ASAP
OH
R R
R R
OH
On the Absolute Configurational Stability of
Bromonium and Chloronium Ions
Scott E. Denmark, Matthew T. Burk, Andrew J. Hoover
J. Am. Chem. Soc. 2010, 132, 1232-1233
R
R
R
X
R
Antoinette Nibbs
Short Literature Presentation
23 August 2010
development of new methods for production of reduced oxygen-content from renewable biomass resources
development of new methods for production of reduced oxygen-content from renewable biomass resources
Deoxygenation of Biomass Polyols
development of new methods for production of reduced oxygen-content from renewable biomass resources
sustainable production of transportation fuels
from biomass in an integrated biomass
production-conversion system
Huber, G. W.; Iborra, S.; Corma, A. Chem. Rev. 2006, 106, 4044-4098
single-flask, solvent-free deoxygenation
procedure to convert glycerol into allyl alcohol
(polymer, 3-hydroxyproionic acid)
Arceo, E; Marsden, P.; Bergman, R. G.; Ellman, J. A. Chem. Commun. 2009, 3357
Prior Art
Me Me
Me Me
OH O O
Cp*ReO , PPh
O 3 3 O
86% bdc
O C H Cl, 125 °C, 80h O
6 5
O OH O
Me Me
Me Me
Cook, G. C. and Andrews, M. A. J. Am. Chem. Soc. 1996, 118, 9448-9449
MeReO (5-10 mol %)
O HO OH 3
or 18-96% yield
H (80-300 psi), 150 °C, THF R R'
R' R R' 2
Ziegler, J. E.; Zdilla, M. J.; Evans, A. J.; Abu-Omar, M. M. Inorg. Chem. 2009, 48, 9998-10000
MeReO or NaReO (5-10 mol %)
O HO OH 3 4
or 4-60% yield
150 °C, solvent, Na SO R R'
R R' R R' 2 3
Vkuturi, S.; Chapman, G.; Ahmad, I.; Nicholas, K. Inorg. Chem. 2010, 49, 4744
Preliminary Experiments
OH O
Re (CO) (2.5 mol %)
2 10
Me Me R H O
Me Me R 2
180 °C, air
OH O
3.5 h
(4S*,4S*)-octane-4,5-diol (50%)
reaction characteristics
•aliquots at intermediate conversion contained the vicinal diketone
•at the early stages, as amount of olefin increased the amount of diketone increased
•upon complete conversion of olefin, depletion and eventual disappearance of diketone
disproportionation reaction?
Disproportionation Reaction
species simultaneously oxidized and reduced to form two different products
•Cannizzaro reaction
•Tishchenko reaction
O OH
R oxidant R reductant R
R R R
O OH
Preliminary Experiments, Part 2
OH
Re (CO) (2.5 mol %)
2 10
HO H O
(CH ) CH (CH ) CH 2
2 11 3 2 11 3
180 °C, air
3.5 h
1,2-tetradenanediol 49%
Re (CO) (2.5 mol %)
2 10
recovered diol
< 170 °C, air
OH
HO
R
Re (CO) (2.5 mol %)
2 10
recovered diol
180 °C, N
2
O OH
R oxidant R reductant R
R R R
O OH
add external alcohol to avoid competing diol oxidation
Reducing Competing Diol Oxidation
Re (CO) or
OH 2 10
BrRe(CO) (2.5 mol %)
5
HO H O
(CH ) CH (CH ) CH 2
2 11 3 2 11 3
temp, air
OH O
R' R'' R' R''
entry catalyst reductant (mL) temp (°C) time (h) yield (%)
1 Re (CO) 5-nonanol (4) 180 3.5 83
2 10
2 Re (CO) 3-octanol (4) 170 4 82 (82)
2 10
3 Re (CO) 3-octanol (5) 170 4 83
2 10
4 Re (CO) 2-octanol (4) 170 3.5 74
2 10
5 BrRe(CO) 3-octanol (4.5) 170 4 84 (85)
5
OH OH OH
Me Me Me Me
Me Me
5-nonanol 3-octanol 2-octanol
use of 9-13 equiv of alcohol afforded complete product in 3.5-4 h
alcohols generated 1-1.5 equiv of ketone
Cp*Re(CO) did not show any activity; BrRe(CO) exhibited similar activity
3 5
Prior Art
Me Me
Me Me
OH O O
Cp*ReO , PPh
O 3 3 O
86% bdc
O C H Cl, 125 °C, 80h O
6 5
O OH O
Me Me
Me Me
Cook, G. C. and Andrews, M. A. J. Am. Chem. Soc. 1996, 118, 9448-9449
MeReO (5-10 mol %)
O HO OH 3
or 18-96% yield
H (80-300 psi), 150 °C, THF R R'
R' R R' 2
Ziegler, J. E.; Zdilla, M. J.; Evans, A. J.; Abu-Omar, M. M. Inorg. Chem. 2009, 48, 9998-10000
MeReO or NaReO (5-10 mol %)
O HO OH 3 4
or 4-60% yield
150 °C, solvent, Na SO R R'
R R' R R' 2 3
Vkuturi, S.; Chapman, G.; Ahmad, I.; Nicholas, K. Inorg. Chem. 2010, 49, 4744