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Maximizing Research Output-Chiral Salens

A Case Study

Dr. S. H. R. Abdi

Technical Director and Ex-Chief Scientist CSIR-
CSMCRI

Synthesis with Catalysts Pvt. Ltd
Sahibabad Industrial Area, Sahibabad Ghaziabad U.P. - India
Schiff base ligands and their metal complexes

Professor H. Schiff at the University Florence
reported the first synthesis of Schiff base
metal complexes as early as the 1860s

H. Schiff, Ann. Chem. Suppl. 3 (1864) 343.
H. Schiff Ann. Chem. 150 (1869) 193.
H. Schiff Ann. Chem. 151 (1869) 186.
Typical Salen ligands and their Complexes

In 1938, T. Tsumaki reported this compound reversibly bound O2,
and this finding led to intensive research on salen and related
ligands for the storage or transport of oxygen
Tokuichi Tsumaki (1938). Bulletin of the Chemical Society of Japan 13: 252–260.
Versatility of the Salen ligand

E. Schulz et al., Dalton Trans., 39 (2010) 6911
Reactive & Functional Polymers 34 (1997) 153-160
Jacobsen’s Epoxidation Catalyst: Virtues and Vices

Substrate approach

H H
N N
Mn
O O
Cl

Virtues Vices

Highly active and enantioselective Requires 50 mol% of expensive 4-
PPYO as co-catalyst
Cheap oxidant: NaOCl N
Non-recoverable
Moderate catalyst loading O
Less enantioselective for trans and
Wide range of olefins 4-PPyO
terminal olefins
E.N. Jacobsen et. al., JACS, 112 (2000) 2081
Our Designed Catalyst

H H
N N
H2 Mn H2
N C O O C N
Cl

H
NC O
NC
H
O Yield, >99%; ee, >99% Time, 5-6 h
O

H O

Yield, >99%; ee, 50%

Co-catalysts: PyNO, PPyNO, DMSO, 1,4-Dioxane, Morpholine-NO, 30 mol%

Journal of Catalysis 209, 99–104 (2002), Tetrahedron Letters 43 (2002) 2665–2668
Catalyst Recyclability Issue

By manipulating solubility of the catalyst

H H H H
N N N N

O
Mn
O
R
O
Mn
O
Tetrahedron: Asymmetry 12 (2001) 433–437
R

Tetrahedron Letters 42 (2001) 2915–2918
J. Mol. Catal A: Chemical 203 (2003) 69–73
Journal of Catalysis 224 (2004) 229–235
H H H H
N N N N
Mn R Mn
O O O O
R

J. Mol. Catal. A: Chemical 218 (2004) 141–146

H H H H
Co-catalyst, PyNO
N N N N
Mn R Mn R
O O
R
O O
R
Epoxide Yield, Quantitative in 2-6h
Ee= 50->99%
n n

Oxidants studied: NaOCl, H2O2,
n= 10-12
R= H, CH 3
Urea. H2O2, Oxone
Worked well for 5 recycle experiments
Heterogenization of Mn(III)salen on Inorganic Supports

On Montmorillonite Clay

H H
N N
H2 Mn H2
N C O O C N
Cl
Cl Cl

Styrene oxide 69%; ee 70% in 7 h
Styrene oxide 99%; ee 45% in 4h (Homo)
Indene Conversion 96%; ee 65% in 10h
Chromene conversion 99%; ee 82% in 6h
NO2-Chromene Conversion 99%; ee 95% in 8h
CN-Chromene Conversion >99%; ee 93% in 8h
Catalyst recycle experiments: 4 cycles with
complete retention of activity and selectivity

Catalysis Letters Vol. 91 (2003) 207-210 Journal of Catalysis 221 (2004) 234–240
Chiral Mn-Salen embedded in nitrogen rich
organic polymer

ChemPlusChem, 2015, 80, 1038-1044
Chiral Salen ligands complexed with different metal ions

H H H H
N N N N
M R M
O O O O
R

HKR
HO OH
Co Catalyst, H2O O +
O
R R
R
(S)-epoxide (R)-diol
Racemic epoxide
Yield 49% Yield 43%
R=CH2Cl, CH3, Ph ee 97% ee 92%

Journal of Molecular Catalysis A: Chemical 179 (2002) 73–77
CHIRALITY 17:590–594 (2005)

Catal. Sci. Technol. 2014, 4, 3899-3908
Asymmetric
sulphoxidation

RSC Adv., 2015, 5, 47732-47739
Synthesis of chiral cyclic carbonates

Catal. Commun., 2015, 61, 78-82
Oxidative Kinetic Resolution
OH O
OH
MnSalenPhI(OAc)2 Conversion 62%; ee up to 99%
+
CH2Cl2, KBr, RT
J. Mol. Catal. A: Chemical 274 (2007) 120–126,
( ) (R)
CHIRALITY 19:352–357 (2007)

Aminolytic Kinetic Resolution R2
R2
R1
O Cr Salen O
R + R +
H N R
Ph Ph
R1 CH2Cl2, RT Tetrahedron: Asymmetry 17 (2006) 1638–1643;
NH2 Ph OH
CHIRALITY 19:809–815 (2007)
( ) (R,R)
(S,R)

R= Ph, CH3 Yield 30% Yield 68%
ee 98% ee 60%

Yield, 69%, ee up to 68%

CHIRALITY 19:82–88 (2007)

RSC Adv., 2016, 6, 7693-7700
Addition of NO2 across C=N and C=O bonds

ChemPlusChem 2014, 79, 1138-1146

RSC Adv., 2015, 5, 99951-99958 Applied Catalysis A: General; 2012, 439–440, 74-79
Cyanation reaction
CN
CHO OAc
V(V) / Ti(IV)
+ Ac2O + KCN/NaCN R3 R1
R3 R1 CH Cl , -20 oC
2 2 R2
R2

Conversion >99%, ee up to 95% 5 times recycled

Eur. J. Org. Chem. 2006, 3175–3180
Tetrahedron: Asymmetry 17 (2006) 2659–2666
J.Mol. Catal. A: Chemical 264 (2007) 140–145

Appl. Catal. A, 2016, 515, 116-125

RSC Adv., 2016, 6, 29977–29982
Synthesis with Catalysts Pvt. Ltd.

Production of:
❖ Precious Metal catalysts
❖ Chiral Ligands and their intermediates
❖ Tailor made catalyst on demand

Services:
❖ Process development for the use of achiral and chiral
catalysts
❖ In-house testing of catalysts particularly chiral and a chiral
hydrogenation, oxidation/epoxidation and Hydrolytic Kinetic
Resolution
❖ Engineering solutions for pilot and production plants
SWC ligand range

For HKR; Co Complexes
For Epoxidation of non-functionalized olefins; Mn-complexes
SWC catalyst range

❖ Ru, Rh, Ir, Pt and Pd based catalysts
❖ Synthesis of metal (precious and non-precious) nano-
particles on Organic and Inorganic supports (as per
demand)
❖ Metal complexes derived from P, P2, OP, NP, N2O2, NO type
ligands
❖ Supports-(Use only)
❖ Organic: activated carbon, urea-cyanuric chloride/glyoxal
polymers/polystyrene/sulphonated polystyrene and related polymers
❖ Inorganic: Basic: LDH (hydrotalcite), MgO, Na-Y-zeolite, basic
alumina; acidic:H-beta zeolite, acidic alumina, zirconia/sulphated
zirconia, sulphonated silica (orano-inorganic hybrids), acids washed
clays like montmorillonite; Neutral/feebly acidic: neutral alumina,
silica, mezoporous silica (MCM-41/SBA-16)