PRIMARY ALCOHOLS FROM TERMINAL PRIMARY ALCOHOLS FROM TERMINAL OLEFINS: FORMAL ANTI-MARKOVNIKOV OLEFINS: FORMAL ANTI-MARKOVNIKOV HYDRATION VIA TRIPLE RELAY CATALYSIS HYDRATION VIA TRIPLE RELAY CATALYSIS Guangbin Dong, Peili Teo, Zachary K. Wickens, Robert H. Grubbs Science 2011, 333, 1609. Shawn K. Collins Shawn K. Collins Universit Université de Montr de Montré al al Department of Chemistry Department of Chemistry Centre for Green Chemistry and Catalysis Centre for Green Chemistry and Catalysis [email protected]Web: Web: http://www.mapageweb.umontreal.ca/collinss/ CHARETTE/COLLINS LITERATURE MEETING CHARETTE/COLLINS LITERATURE MEETING Université de Montréal (UdeM) Université de Montréal (UdeM) March 12 March 12 th th , 2014 , 2014 Montréal, Québec Montréal, Québec
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Shawn K. Collins Universit é de Montr é al Department of Chemistry
PRIMARY ALCOHOLS FROM TERMINAL OLEFINS: FORMAL ANTI-MARKOVNIKOV HYDRATION VIA TRIPLE RELAY CATALYSIS Guangbin Dong, Peili Teo , Zachary K. Wickens , Robert H. Grubbs Science 2011 , 333 , 1609. Shawn K. Collins Universit é de Montr é al Department of Chemistry - PowerPoint PPT Presentation
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PRIMARY ALCOHOLS FROM TERMINAL PRIMARY ALCOHOLS FROM TERMINAL OLEFINS: FORMAL ANTI-OLEFINS: FORMAL ANTI-
MARKOVNIKOV HYDRATION VIA MARKOVNIKOV HYDRATION VIA TRIPLE RELAY CATALYSISTRIPLE RELAY CATALYSIS
Guangbin Dong, Peili Teo, Zachary K. Wickens, Robert H. Grubbs Science 2011, 333, 1609.
Shawn K. CollinsShawn K. CollinsUniversitUniversitéé de Montr de Montrééalal
Department of ChemistryDepartment of ChemistryCentre for Green Chemistry and CatalysisCentre for Green Chemistry and Catalysis
CuCl2 (20 mol %)benzoquinone (80 mol %)iPrOH/tBuOH (1:2), 85 C
OH
77 %
OH
1.3 % 0.7 %
OO
1.4 % 1.5 %
SCOPE
R
Shvo's catalyst (10 mol %)PdCl2(MeCN)2 (10 mol %)
H2O (1.1 eq.)
CuCl2 (20 mol %)benzoquinone (80 mol %)iPrOH/tBuOH (1:2), 85 C
ROH
OH
84 %
OH
42 %
OH
61 %
OH
60 %
OH
72 %
OH
75 %
OH
72 %
OH
63 %
OH
83 %
OH
74 %Cl FBr O2N
F3C
CF3
OHOH
56 % 12 %
>20 : 1 >20 : 1 >20 : 1 >20 : 1 >20 : 1
>20 : 1>20 : 1>20 : 1>20 : 1>20 : 1
1 : 1.4 1 : 2.1
SUMMARY.
Compared to the classic hydroboration/oxidation sequence, our approach is still far from perfect, with its relatively high catalyst loadings and use of stoichiometric BQ. However, we are strongly encouraged by the excellent selectivity with arylsubstituted olefins, initial promising results with aliphatic alkenes, and the facile recovery of BQ to reduce the overall expense. Despite being in its infancy, this methodology has demonstrated great potential and will stimulate ongoing research in the field of olefin hydration
EXTENSION TO HYDROAMINATION
NMePh1) PdCl2(PhCN)2 (10 mol %)
BQ (1 eq.), H2O, t-BuOH, 35 C
2) N-Me aniline (2.5 eq.) Ir catalyst (10 mol %)
5:2 formic acid:TEA azeotrope, 85 C66 %
N
MeO
OMe
Ir Cl
Bronner, S. M.; Grubbs, R. H. Chem. Sci. 2014, 5, 101.