“Catalyst-on-a-Tape”—Teflon:

A New Delivery and Recovery

Method for Homogeneous Flu

orous Catalysts

Latest CENsLatest CENs

Biffis, A. et al. Org. Lett. 1998, 7, 1841

“fluorous ponytails” : (CH2)m(CF2)n-1CF3

Horvath, I. T. et al. Acc. Chem. Res. 1998, 31, 641

Co-cat : Co{OOC(CH2)2(CF2)7CF3}2 ; C6F14 : $17.6 (10ml)

Ru-cat : K[Ru(C7F15COCHCOC7F15)2] ; C8F14Br : $45 (1 g)

liquid/liquid phase separation

Dinh, L. D. et al. New. J. Chem. 2005, 29, 173

Catalyst-on-a-Tape

Reaction for four cycles

As opposed to lAs opposed to leaching eaching

Some intrinsic Some intrinsic problem with thproblem with the recycling mete recycling methodhod

Effect of TeflonEffect of Teflon

(a) All reactants

except PhMe2SiH are added; (b) The mixture is heated to 55 °C; (c) The tape is removed; (d) The PhMe2SiH is

added.

ResultsResults

“catalyst-on-a-tape” 的系統提供了許多反應上的好處，也可以減少對環境的污染。

氟的化合物提供一個最合適的反應條件或適用於某些特定的反應，可以應用在工業上面。

Synthesis for catalystSynthesis for catalyst

Gladysz, J. A. et al. J. Am. Chem. Soc. 1999, 121, 2696

including the homogeneous oxidation of alcohols and alkenols and the epoxidation of alkenes." Friedel-Crafts acyl Friedel-Crafts acylations and esterifications. ations and esterifications.

a chelating solvent such as tetrahydrofuran (THF) Reactions can be catalyzed under monophasic condition

s at the high-temperature limit, and the products and catalyst can be separated under biphasic conditions at the low-temperature limit

highly electron-withdrawing perfluoroalkyl groups

C6F6/CF3C6H5 solution

PhSiH(Me)PhSiH(Me)2 2 : moisture sensitive(5g/$20): moisture sensitive(5g/$20)

Oxidative additionOxidative addition

LnM + A B LnM

16e 18e

A

B

oxidative addition

EpoxidationEpoxidation

Epoxide Carboxyic acid

CC +RCOOH

O C C

O+

RCOH

O

EsterificationEsterification

+R'COH

OROH

H+

R'COR

O+ H2O

Friedel-Crafts acylationsFriedel-Crafts acylations

H+

CH3CH2CCl

O AlCl3

40oC

CCH2CH3

O

+ HCl