HYDROGENATION OF KETONES WITH Cp*Rudiamine CATALYST - - PowerPoint PPT Presentation

▶
hydrogenation of ketones with cp ru diamine catalyst
SMART_READER_LITE
LIVE PREVIEW

HYDROGENATION OF KETONES WITH Cp*Rudiamine CATALYST - - PowerPoint PPT Presentation

Dec 26, 2023 633 likes •731 views

HYDROGENATION OF KETONES WITH Cp*Rudiamine CATALYST Cp*RuCl(cod) O OH (CH 3 ) 2 N(CH 2 ) 2 NH 2 KOH H 2 + 2-propanol 1 atm 30 C, 1 h 100% yield ketone:Ru:diamine:KOH = 100:1:1:1 N H Ru N H R' H C O R

slide-1
SLIDE 1

HYDROGENATION OF KETONES WITH Cp*Ru–diamine CATALYST

O OH 2-propanol H2 + ketone:Ru:diamine:KOH = 100:1:1:1 30 °C, 1 h 100% yield 1 atm Cp*RuCl(cod) (CH3)2N(CH2)2NH2 KOH 日本化学会第7 6 春季年会, 3B614(1999) N Ru N H H H R C R' O

slide-2
SLIDE 2

Kwiatek, Mador, Seyler, J. Am. Chem. Soc., 1962, 84, 304. C6H5 C6H5 + S/C = 100, [ketone] = 0.1 M Fujitsu, Mochida, J. Org. Chem., 1981, 46, 2287.

HYDROGENOLYSIS OF EPOXIDES WITH HOMOGENEOUS CATALYSTS

[Rh(nbd)(P(C2H5)3)2]+ O H2 1 atm OH C6H5 O n 90% conv + C6H5 C6H5 + S/C = 2.9, [ketone] = 0.34 M K3[Co(CN)5] O H2 1 atm OH 53% conv TOF = 0.64 h–1 diglyme–H2O 3 : 1 C6H6–H2O, r.t. 28 °C, 6 h

slide-3
SLIDE 3

LIGAND ACCELERATION IN HYDROGENOLYSIS OF EPOXIDES

2-propanol H2 + Cp*RuCl(cod) ligand KOH 10 atm 30 °C, 2 h ketone:Ru:ligand:KOH = 100:1:1.5:1 OH OH branch/linear NH2 (CH3)2N (C6H5)2P N(CH3)2 NHCH3 (C6H5)2P >99/1 >99/1 (C6H5)2P P(C6H5)2 P(C6H5)3 C6H5CH2NH2 + NH2 (C6H5)2P 89/11 <1% 0% 63% conv 15% 5% <1% ligand: O +

slide-4
SLIDE 4

HYDROGENOLYSIS OF TERMINAL EPOXIDES

R OH 2-propanol H2 + substrate:Ru:ligand:KOH = 100:1:1.5:1 50 °C, 18 h Cp*RuCl(cod) (C6H5)2P(CH2)2NH2 KOH R 100% conv + R OH 90% conv 100% conv 99% conv 99% conv 10 atm branch/linear 89/11 >99/1 >99/1 98/2 >99/1 C6H5 O O C6H5 O O O C6H5 O substrate: O intact

slide-5
SLIDE 5

P Ru H N H O Ar Ar

A POSSIBLE MECHANISM

Ru HN P Ar Ar Ru H H

2

N Ar Ar P P Ru HN Ar Ar H H C6H5 O C6H5 C6H5 OH H2 H Cp*RuCl(cod) KOH (C6H5)2P(CH2)2NH2 + +

slide-6
SLIDE 6

HYDROGENOLYSIS OF (S)-STYRENE OXIDE

OH 2-propanol H2 + 50 °C, 18 h Cp*RuCl(cod) (C6H5)2P(CH2)2NH2 KOH OH 10 atm 0% ee substrate:Ru:ligand:KOH = 100:1:1.5:1 O + 89 : 11 100% conv 96% ee

slide-7
SLIDE 7

RACEMIZATION OF CHIRAL ALCOHOLS

OH 2-propanol 50 °C, 30 min Cp*RuCl(cod) (C6H5)2P(CH2)2NH2 KOH 0% ee 99% ee OH S/C = 100 solvent effect 2-propanol > ethanol > methanol

slide-8
SLIDE 8

HYDROGENOLYSIS OF (S)-STYRENE OXIDE IN VARIOUS SOLVENTS

OH solvent H2 + 50 °C Cp*RuCl(cod) (C6H5)2P(CH2)2NH2 KOH OH 10 atm substrate:Ru:ligand:KOH = 100:1:1.5:1 O + 96% ee solvent conv, % branch/linear ee, % time, h 2-propanol methanol ethanol 1 2 18 79 64 64 89/11 90/10 96/4 81 84

slide-9
SLIDE 9

Hydrogenation of ketones

Cp*Ru(II) COMPLEXES BEARING PRIMARY AMINE LIGANDS

Hydrogenolysis of epoxides Racemization of secondary alcohols N Ru P H H H CH2 O N Ru N H H H R C R' O R Ar Ar