Cross-Coupling Chemistry in Continuous Flow - New Trends in Cross-Coupling: Theory and Applications - page 617

XPhos precat (0.05 - 0.2 mol %)
XPh os (0.05 - 0.2 mol %)

HetAr-X +

Ar 'B( OH ) 2 Ar -Ar'

1equiv 1.5equiv K 3 PO 4 (2 equiv), TBAB (10 mol %)

NMP/toluene/H 2 O(4:1:5),60°C

O

S

O

MeO N

Me

S

O

N

CF 3

X= Cl
0.05 mol % precat
0.05 mol % XPhos
99% yield

X= OTf
0.2 mol % precat
0.2 mol % XPhos
84% yield

X= OTf
0.2 mol % precat
0.2 mol % XPhos
82% yield

PCy 2

i -Pr i -Pr

Pd N H 2

XPhos Cl

i -Pr

XPhos precat XPhos

Figure 13.4 Biphasic Suzuki-Miyaura cross-coupling reactions in a micro packed-
bed reactor.

Fluorous-tagged Catalyst:

Fluorous Tail

Catalyst

Me

F 2
C

F 2
C

F 2
C

Me N

CF 3

N F 2 F 2 F 2 F 2

Me N

Pd(OAc) 2

Me

Segmented F low:

fluorous phase

aq. droplet aq. droplet aq. droplet

aq.

catalyst

fluorous
tail

Figure 13.5 Fluorous-tagged Pd-catalyst for the continuous flow biphasic Suzuki-
Miyaura reaction with catalyst recycling.

catalyst was oriented towards the aqueous droplet and allowed a Suzuki-
Miyaura reaction to be catalyzed. The catalyst could be recycled four times
without diminished activity. The extent of leaching of the catalyst into the