Organic Chemistry Frontiers This journal is activation ... · pathway Ar Scheme S1 The Pd-catalyzed...

Supplementary Material (ESI) for Organic Chemistry FrontiersThis journal is The Royal Society of Chemistry 2012○C

S1

One-step rapid synthesis of π-conjugated large oligomers via C–H activation couplingShi-Yong Liu,*ab Di-Gang Wang,b Ai-Guo Zhongb and He-Rui Wen*a

aSchool of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, P. R. Chinab Department of Pharmacy & Chemistry, Taizhou University, Taizhou 317000, P. R. China

Contents

1. Figs. S1 .......................................................................................................................................S2

2. Scheme S1...................................................................................................................................S2

3. Fig. S2 and 3..............................................................................................................................S3

4. Fig. S4 ........................................................................................................................................S4

5. Fig. S5..........................................................................................................................................S5

6. Fig. S6..........................................................................................................................................S6

7. Fig. S7 .........................................................................................................................................S7

8. 1H and 13C NMR, and Maldi-TOF MS spectra.......................................................................S8-22

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2017


S2

PAr2

Pd

Ar2P

Pd

O O

CH3

CH3

OO

Ar = o-CH3(C6H4)

Herrmann-Beller catalyst

O

PdPdPd2(dba)3

3

P

PCy3

P

OCH3

OCH3

H3CO

P(o-MeOPh)3

Fig. S1 The molecular structures of Herr Pd, Pd2(dba)3, PCy3 and P(o-MeOPh)3.

[Pd0]

[PdII]Ar'

X

H, basebase HX

Ar'Ar

[PdII]Ar

Ar'

Ar'X

PdIIB2H2

2 HBPdAr Ar

Ar

Transmetallation+

Reductive elimination

ArH Ar'X+ Ar Ar'PdIIB2

-HX

B = Cl, -OAc, etc

Ar

Ar

Ar

Overall reaction

Transformation of PdII pre-catalyst to Pd0 catalyticspecies

C-H/C-H homo-coupling side product

C-H activaion

Oxidative additionReductive

elimination

Pd

O

Ar'

L

O

R

H -RCOOHAr'Pd(L)ArO

O

HAr

Pd

R

L

Ar

The Palladation ofC-H bond via CMDpathway

Ar

Scheme S1 The Pd-catalyzed DA reaction, the reduction of PdII pre-catalyst to Pd0 catalytic species, the catalytic cycle of the DA coupling, and the palladation of C-H bond.


S3

LigandNon- ligand

Starting DPP

p- B (DPP)2

Non- ligand Ligand

Fig. S2 The reaction between DPP and p-dibromobenzene with and without ligand P(o-MeOPh)3 using toluene as reaction medium (entries 10 and 11 in Table 1). Digital photos of (a) The reaction mixtures after reacting for 12 h and cooling to room temperature. (b) The TLC analysis of both reaction mixtures, using CH2Cl2 : hexane (2:1, v/v) as eluent, and the spots marked with green and red frame are the reactant DPP and target product p-B(DPP)2, respectively.

Starting DPP

p- B- (DPP)2

Fig. S3 The TLC analysis of the reactions between DPP and p-dibromobenzene (left) or p-diiodobenzene (right). (see Entries 12 and 13 in Table 1). The spots marked with green and red frame are the reactant DPP and target product p-B(DPP)2, respectively.


S4

p- B- (DPP)2 m- B- (DPP)2

di- Br- Ph- DPP

DPP- DPP- DPPo- B- (DPP)2 TB- (DPP)3 Py- (DPP)4 TBE- (DPP)4 SF- (DPP)4

Fig. S4 Digital photos of TLC analysis of the synthetic reactions for the eight oligomers. From left to right are respectively p-B-(DPP)2, m-B-(DPP)2, o-B-(DPP)2, DPP-DPP-DPP, TB-(DPP)3, Py-(DPP)4, TBE-(DPP)4 and SF-(DPP)4. For all the TLC plates, the spots on the left are the starting DPP, and the spots marked with red dotted frames are the target oligomers.


S5

Max = 567 nm

S

N

N

O

O

R

R

SS

R

R

O

O

N

N

S

Max = 577 nm

S

R

R

O

O

N

N

SS

N

N

O

O

R

R

S

Max = 579nm

S

N

N

O

O

R

R

S

S

NN

O

O

RR

S

S N

N

O

O

R

RS

Max = 596 nm

S

R

R

O

O

N

N

SS

N

N

O

O

R

R

S

R =C6H13

C8H17

< =.

<

Fig. S5 The shortest pathways of π-electron delocalization (marked with blue color) of the phenyl-cored DPP-based oligomers o-B-(DPP)2, m-B-(DPP)2, p-B-(DPP)2 and TB-(DPP)3, and the corresponding normalized Uv-vis spectra (below).


S6

o- B- (DPP)2 m- B- (DPP)2

TB- (DPP)3p- B- (DPP)2

Fig. S6 DFT optimized geometries of phenyl-cored DPP-based oligomers, o-B-(DPP)2, m-B-(DPP)2, p-B-(DPP)2 and TB-(DPP)3 (the alkyl chains replaced by methyl groups).


S7

S

N

N

O

O

R

R

S

S

R

R

O

O

N

N

S

S

N

N

O

O

R

R

S

S

R

R

O

O

N

N

S

Max = 570nmN

S

R

R

O

O

N

NN

S

N

N

O

O

R

RS

O

O

R

R

S

S

S

SS

R

R

O

O

N

N

twisted

Max = 584nm

S

N

N

O

O

R

R

S

SN

N

O

O

R

S

SN

N

O

O

R

R

S

S

N

N

O R

R

S

O

R

Max = 596nm

< <

Fig. S7 The shortest pathways of π-electron delocalization (marked with blue color) of the Py-, TBE- and SF-(DPP)4 oligomers, and the corresponding normalized Uv-vis spectra (below).


S8

Fig. S8 The Uv-vis spectra of the starting DPP, oligomers o-B-(DPP)2, m-B-(DPP)2, TB-(DPP)3, p-B-(DPP)2, Py-(DPP)4, TBE-(DPP)4 and SF-(DPP)4 in CHCl3 at concentrations of 4.54, 2.54, 2.03, 1.55, 2.16, 1.89, 1.07, 1.69 and 1.27 ×10-5 mol/L.

Table S1 The extinction coefficients of the DPP materials at λmaxs (×104 M-1 cm-1).

DPP o-B-(DPP)2 m-B-(DPP)2 p-B-(DPP)2 TB-(DPP)3 DPP-DPP-DPP

Py-(DPP)4

TBE-(DPP)4

SF-(DPP)4

2.02 4.47 5.82 4.38 6.94 7.12 12.61 12.74 14.08


S9

Fig. S8 The 1H and 13C NMR spectra of p-B-(DPP)2 in CDCl3.


S10

Fig. S9 The 1H and 13C NMR spectra of m-B-(DPP)2 in CD2Cl2.


S11

Fig. S10 The 1H and 13C NMR spectra of o-B-(DPP)2 in CD2Cl2.


S12

Fig. S11 The 1H and 13C NMR spectra of DPP-DPP-DPP in CDCl3.


S13

Fig. S12 The 1H and 13C NMR spectra of TB-(DPP)3 in CDCl3.


S14

Fig. S13 The 1H and 13C NMR spectra of Py-(DPP)4 in CD2Cl2.


S15

Fig. S14 The 1H and 13C NMR spectra of TBE-(DPP)4 in CD2Cl2 and in CDCl3, respectively.


S16

Fig. S15 The 1H and 13C NMR spectra of SF-(DPP)4 in CD2Cl2.


S17

1572.433

881.4691678.507

0

1000

2000

3000

4000

Inte

ns. [

a.u.

]

1000 1500 2000 2500 3000 3500m/z

Fig. S16 The MALDI-TOF MS spectrum of p-B-(DPP)2, calcd. 1572.51, found 1572.43.


S18

1572.311

0

100

200

300

400

500

Inte

ns. [

a.u.

]

1000 1200 1400 1600 1800 2000 2200m/z

Fig. S17 The MALDI-TOF MS spectrum of m-B-(DPP)2, calcd. 1572.51, found 1572.31.

1572.639

0

1000

2000

3000

4000

5000Inte

ns. [

a.u.

]

1000 1200 1400 1600 1800 2000 2200m/z

Fig. S18 The MALDI-TOF MS spectrum of o-B-(DPP)2, calcd. 1572.51, found 1572.64.


S19

Fig. S19 The MALDI-TOF MS spectrum of DPP-DPP-DPP, calcd. 2007.13, found 2007.82.


S20

Fig. S20 The MALDI-TOF MS spectrum of TB-(DPP)3, calcd. 2319.71, found 2319.77.


S21

Fig. S21 The MALDI-TOF MS spectrum of Py-(DPP)4, calcd. 3191.05, found 3191.63.


S22

Fig. S22 The MALDI-TOF MS spectrum of TBE-(DPP)4, calcd. 3321.34, found 3321.30.


S23

Fig. S23 The MALDI-TOF MS spectrum of SF-(DPP)4, calcd. 3305.20, found 3305.50.

Organic Chemistry Frontiers This journal is activation ... · pathway Ar Scheme S1 The Pd-catalyzed...

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