István T.

Horváth - BMEVEKFM210

ENVIRONMENTALLY BENIGN AND CATALYTIC PROCESSES

KFM210
2020-21, Fall Semester, Friday 8:30 – 11:00

ORGANOCATALYSIS

István T. Horváth

Department of Chemical and Environmental Process Engineering

istvan.t.horvath@edu.bme.hu
istvan.t.horvath@att.net

ORGANOCATALYSIS

• Novel synthetic strategy in organic chemistry.

• Small organic molecules are used as catalysts.
• Environmentally friendly approach.
• Balance between activity and selectivity.

O O O
1 COOH
N
H (1)
99 % O
O OH
93% ee

Hajos–Parrish–Eder–Sauer–Wiechert reaction

1
István T. Horváth - BMEVEKFM210

ORGANOCATALYSIS
1 COOH
O O N O OH
+ H (2)
R1 30 mol % kat. R1
DMSO, 25oC
hozam: 54-97%
R1= Alkil, aril ee : 60- 96%
List, B.; Lerner, R. A.; Barbas III, C. F. J. Am. Chem. Soc. 2000, 122, 2395-2396.

R2
R3 O O

OH R1 R1
N COOH R2
H
O
COOH
N OH N
OH OH
R2
R1 R1
R2
R3 OH

O
COOH
N N
OH
R2
R1 R1
R2
R3 OH
iminium ion
iminium ion O R3CHO
COOH
R3 O N H O N

R1 R1
H
R2 R2
enamin

PROLINE AS CATALYST

1 COOH
O O N O OH
+ H
R1 30 mol % kat. R1
OH DMSO, 25oC OH
2 3 4
termelés: 40-95%
ee : 70-97%

1 COOH
O O N O OH
+ H
R2 10 mol % kat. R2
R1 DMF, 4oC R1
5 6 7
termelés: 75-88%
R2= nem enolizálható
ee : 91-99%

2
István T. Horváth - BMEVEKFM210

PROLINE AS CATALYST
COOH COOEt
O COOEt N O HN
+ N H N
R1 N 10 mol % kat. R1 COOEt
R2 EtOOC CH3CN, 25oC R2
R1 = H, alkil termelés: 67-92%
ee : 79-99%

COOH
O N O HN
+ N H O
H O Ph 5 mol % kat.
R CHCl3, 4oC R

termelés: 60-95%
ee : >97%

A SYN SELECTIVE CATALYST

CF3
O S O
NH

NH

O O OH O
5 mol%
Ar NMP, 25 oC
Bu Bu
Ar = 4-NO2C6H4 syn:anti >20:1
99% ee (syn)
77% termelés

O
O CF3
CF3 N S
N S O
H O N O H
N
O
Ar H
Ar H Bu
Bu

anti enamin syn enamin

3
István T. Horváth - BMEVEKFM210

MANNICH REACTIONS
OMe
MeO
COOH
O N O HN
N H
+
5 mol % kat. COOEt
H COOEt
R dioxán, 25oC R

termelés: 57-81%
dr (syn/anti) 3:1 - 19:1
ee : 93-99% ee

OMe
OMe
MeO O HN
O COOEt
O HN
N (S) vagy (R)
+
30 mol % kat. COOEt
H COOEt
dioxán, 25oC

ee : 94% ee

ORGANOCATALYSIS

ADVANTAGES

Non-toxic, environmentally friendly

Low cost
Robust
Metal-free