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: 252260.
 Versatility of the Salen ligand

E. Schulz et al., Dalton Trans., 39 (2010) 6911

Reactive & Functional Polymers 34 (1997) 153-160
 Jacobsens 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, 99104 (2002), Tetrahedron Letters 43 (2002) 26652668

 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) 433437
R

Tetrahedron Letters 42 (2001) 29152918

J. Mol. Catal A: Chemical 203 (2003) 6973
Journal of Catalysis 224 (2004) 229235
H H H H
N N N N
Mn R Mn
O O O O
R

J. Mol. Catal. A: Chemical 218 (2004) 141146

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) 234240
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) 7377

CHIRALITY 17:590594 (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) 120126,
( ) (R)
CHIRALITY 19:352357 (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) 16381643;
NH2 Ph OH
CHIRALITY 19:809815 (2007)
( ) (R,R)
(S,R)

R= Ph, CH3 Yield 30% Yield 68%

ee 98% ee 60%

Yield, 69%, ee up to 68%

CHIRALITY 19:8288 (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, 439440, 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, 31753180

Tetrahedron: Asymmetry 17 (2006) 26592666
J.Mol. Catal. A: Chemical 264 (2007) 140145

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

RSC Adv., 2016, 6, 2997729982

 Synthesis with Catalysts Pvt. Ltd.

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Precious Metal catalysts
Chiral Ligands and their intermediates
Tailor made catalyst on demand

Services:
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catalysts
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Resolution
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 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)
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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,
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