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Njomza Ajvazia and Stojan Stavbera,b,c
a Jožef Stefan International Postgraduate School, Jamova 39,
Ljubljana, Slovenia
b Jožef Stefan Institute, Jamova 39, Ljubljana, Slovenia
c Centre of excellence for integrated approaches in chemistry and
biology of proteins, Jamova 39, Ljubljana Slovenia
Amsterdam , March 2017
Comprehensive transformation of alcohols catalyzed by N-halo compounds under green
reaction conditions
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1. Introduction
• Methods for the transformation of organic
compounds following the principles of green
chemistry challenging tasks in organic
synthesis.
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1. Introduction
• Organic solvents-blacklisted!! human health
and environment.
• Solvent-free synthetic methods - laboratory
synthesis and chemical industry simplicity and
cost efficiency.
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1. Introduction
• Alcohols transformation under green reaction
conditions - useful building block in organic
synthesis.
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• Metal: InCl3, (La, Yb, Sc, Hf triflate), BiCl3
• Brønsted acid: TfOH, H2SO4, HClO4
• Lewis/Brønsted combination: FeCl3•6H2O
mediated by TsOH
Metal
I2
Bronsted acid
1. Introduction
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• DISADVANTAGES of general synthetic methods:
solvent (environmentally unfriendly)
high temperature
long reaction time
high amount of catalyst
1. Introduction
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2. Aim of the work
New methodologies for comprehensive direct
transformation of various alcohols principles of
green chemistry, especially catalytically supported
transformations under solvent-free reaction conditions
(SFRC) or high substrate concentration reaction conditions
(HCRC).
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[1] (a) B. P. Bandgar, L. S. Uppalla, V. S. Sadavarte, Synlett 2001, 2001, 1715-1718; (b) S. T. Kadam, S. S. Kim, Catal. Commun. 2008, 9, 1342-1345; (c) B. Karimi, G. R. Ebrahimian, H. Seradj, Org. Lett. 1999, 1, 1737-1739.
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3. Various transformations of alcohols catalytically
supported by N-halo organic compounds
C-O bond formation
Figure 1.1 The catalytic effect of N-halo catalysts on conversion of
diphenylmethanol 1 with MeOH under HCRC.
0
20
40
60
80
100
NFSi FTEDA NBS NCS NIS
27 32
92 92
100
3 3
5 5
Re
lati
ve d
istr
ibu
tio
n [
%]
N-halo catalysts
Symmetric ether 3
Methyl ether 2
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Scheme 1.1: Transformation of benzyl and tertiary alkyl alcohols with alkyl or benzyl alcohols in the presence of N-halo catalysts under SFRC or under HCRC.
• Structures and yields [%] of products:
97% 99% 90%
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64% 89% 88%
73% 90%
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0
20
40
60
80
100
NCS FTEDA NBS NFSi NIS
4
27
100
4
48
Re
lati
ve d
istr
ibu
tio
n [
%]
N-halo catalysts
Symmetric ether 3
2-Benzhydryl-1,3-diphenylpropane-1,3-dione 5
Figure 1.2: The effect of substoichiometric amount of N-halo catalysts
on conversion of diphenylmethanol 1 with dibenzoylmethane 4 under
SFRC.
C-C bond formation
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Scheme 1.2: Reactions of β-dicarbonyl compounds with different alcohols catalyzed by NIS under SFRC.
• Structures and yields [%] of products:
98% 99%
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98% 99%
98% 99%
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0
20
40
60
80
100
NCS FTEDA NBS NFSi NIS
100
Co
nve
rsio
n o
f al
coh
ol [
%]
N-halo catalysts
Figure 1.3: The catalytic effect of N-halo catalysts on conversion of
diphenylmethanol with1,2-dihydronaphthalene under SFRC.
C-C bond formation
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Scheme 1.3: Direct coupling of diphenylmethanol and 1,1 diphenylethene
catalyzed by NIS under SFRC.
C-C bond formation
Scheme 1.4: Direct coupling of secondary and tertiary alcohol catalyzed by
NIS under SFRC.
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0
20
40
60
80
100
NFSi NBS NCS FTEDA NIS
51 67
72 76 80
12
8 11
10 5 4
Re
lati
ve d
istr
ibu
tio
n[%
]
N-halo catalysts
1-(p-tolyl)ethanone 9
Symmetric ether 8
N-(1-(p-Tolyl)ethyl)acetamide 7
Figure 1.4: The catalytic effect of N-halo catalysts on
conversion of 1-(p-tolyl)ethan-1-ol 6 in acetonitrile solution.
C-N bond formation
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Scheme 1.4: Direct coupling of diphenylmethanol with 4-bromoaniline catalyzed by NIS under SFRC.
C-N bond formation
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Scheme 3.3: Chlorination of 4-nitrobenzyl alcohol with TMSCl catalyzed by NIS under SFRC.
C-Cl bond formation
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Scheme 1.5: Isothiocyanation or ethoxylation of phenyl(p-tolyl)methanol with TMSNCS or TMSOEt catalyzed by NIS under SFRC.
Scheme 1.6: Trimethylsilylation of phenyl(p-tolyl)methanol with TMSCN catalyzed by NIS under SFRC.
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8. Conclusions
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The presented methodology is new, highly efficient and
easy to perform approach to the synthesis of
comprehensive type of derivatives starting from hydroxyl
functional group targets and applying solvent-free reaction
conditions or high substrate concentration reaction
conditions as green chemical reaction protocol.
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Acknowledgments
• Slovene Human Resources Development and Scholarship
Fund and the Slovenian Research Agency through the
programme Chemistry for Sustainable Development
• Prof. Dr. Stojan Stavber
• Slovenian NMR Centre at the National Institute of Chemistry,
Ljubljana, Slovenia
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THANK YOU FOR YOUR ATTENTION!