The document summarizes the synthesis of several compounds. Key reactions include: 1) Synthesis of (R)-BE from (R)-BINOL involving esterification. 2) Synthesis of (R)-BEBP and (R)-CBEBPB involving substitution, bromination and addition of PF6 groups. 3) Synthesis of PPB and (R)-BBEBPP involving substitution and addition of PF6 groups. 4) Synthesis of monomer (R)-DBB involving bromination and esterification. 5) Polymerization of (R)-DBB to form P1, P2 and P3 polymers.

1. Compounds I synthesized in the past.
Postdoctoral Synthesis.
OC 10H 21
OC10 H21
Si Si I OH
OC 10H 21 H21 C10O
OC10 H21 OC10 H21 O
I I + H H + I O
H21 C10O H21C10O
O OC10H21 O
O O
n
H21C10O
P PE 1
OCH3 OCH3
OH O(CH2 )11OH
I
I I I O
I + Fe
I
HO11(CH 2 )O Cl
OCH3 OCH3 HO
O
Fe
O(CH2 )11O OC 10 H 21 O
I I + H H + I O
O11(CH 2 )O H 21 C 10 O
Fe O
Fe
O
O
O OC 10 H 21 O ( )10 OC10 H21 O
O O
n
H 21 C 10 O O H21 C10O
O ( ) 10
O
Fe
PP E2
1

2. OH O O
OC10H 21 O
I
+ H H + I O
I
OH O O H21C 10O
O OC 10 H21 O OC10H 21 O
O O
n
H 21 C10 O O H21C 10O
PPE3
Scheme 1. Synthesis of poly (para-phenyleneethynylene)s.
S Br S
TMS S
OC 6H 13
OC 6H 13 OC 6H 13 TMS
S
I I I TMS H13 C6 O
H 13C 6O H 13C 6O
OC 6H 13
S OC 6H 13
H13C 6O
H TMS
S 2
OC 6H 13
H13C6O
I TMS
S
H13C 6O
OC 6H 13
H H
S 2
OC 6H 13
H13C 6O
H TMS
OC 6H 13 S 4
I TMS H13C 6O
S 2
H13C 6O
2

3. Br I Br TMS I TMS
S
TMS
S
TMS
I S
TMS H
S 2 H S 2
H
. Scheme 2. Synthesis of oligo [(para-phenyleneethynylene)-alt-(2,5-thienyleneethynylene)]s.
I TMS
Br I Br TMS
Br
Br TMS I TMS H TMS
2 2 3
H H
3
Scheme 3. Synthesis of oligo (para-phenyleneethynylene)s.
3

4. + I N N
S S
N
I S
OC 6H 13 OC 6H 13
+ I N N
S S
H 13C 6O H 13C 6O
OC 6 H13
N
I S
H13C 6O
Scheme 4. Synthesis of short molecular wire with pyridyl.
4

5. SMT TMS SMT TMS
N N
O H
+ TMS N N N Zn N
N H H
H N N
SMT TMS SMT TMS
N N
H
N N N Zn N
H
N N
SMT TMS SMT TMS
N N
H
O
+ TMS N N N Zn N
N H H
H N N
SMT TMS SMT TMS
N N
H
N N N Zn N
H
N N
I I I I
N N
O H
+ I N N N Zn N
N H H
H N N
I I I I
Scheme 5. Synthesis of porphyrin derivatives.
5

6. N
H 13C6O
N Zn N + TMS
I S
N
O C6H 13
SMT TMS
H 13C 6O H 13C6O
OC 6H13 OC 6H 13
OC 6H13 OC 6H13
H 13C6O S H 13C 6O S
S S
N N
N N
Zn Zn
N N
N N
S S
OC 6H 13 OC 6H13
S S
H 13C6O H 13C6O
H13C 6O H 13C6O
OC 6H13 OC 6H 13
TMS
S MT
SMT TMS
S
S
N
N N
Zn
N
N Zn N + TMS N
I S
N
S
S
TMS
SMT
Scheme 6. Synthesis of cross-shaped π–conjugated meso-alkynyl porphyrin derivatives.
6

7. SMT TMS
OC 6H 13 H13C 6O OC6 H13 H 13C6O
H 13C 6O OC6 H13 H13C 6O OC6H 13
N OC 6H 13 N N
N Zn N + I TMS N Zn N N Zn N
N N N
H13C 6 O
H 13C 6O OC6H 13 H13C 6O OC 6H 13
OC 6H 13 H13C 6O OC6 H13 H 13 C6 O
SMT TMS
SMT TMS
OCH 3 H 3CO
H3 CO OCH 3
N OCH 3 N
N Zn N + I TMS N Zn N
N N
H 3CO
H3 CO OCH3
OCH 3 H 3CO
SMT TMS
Scheme 7. Synthesis of π–conjugated meso-alkynyl porphyrin derivatives.
7

8. N
OC 6H 13
N Zn N + TMS
I S
N
H 13 C6O
TMS
SMT
OC6 H13
OC 6H 13
H 13 C6 O OC6 H13
C6 H13 O H 13 C 6O OC 6H 13
H 13 C6 O
S
S
S
S
N
N
N
Zn N N
Zn
N
N
N
S
S
S
S
OC6 H13 OC6 H 13
H13C 6 O OC6 H 13 OC 6H 13
H 13 C6 O
H13C 6 O
TMS H 13 C6 O
SMT
Scheme 8. Synthesis of cross-shaped π–conjugated meso-phenyl porphyrin derivatives.
8

9. H
H S
S
I I
n
n
N N
H H
N N + H N N
H H S n H
N N
n = 1, 2
I n
I n
S
H
S
n = 1, 2
H H
H S
S
n
n
N
N Zn N
N
n
n
S
H
S
n = 1, 2
H
9

10. H
H
S
S
OC 6H 13 H 13C6O
H13C 6O
O C6H 13
I I
n
n
N H13C 6O
H N
H
N N + H N N
H S H H
N n N
OC 6H 13
n = 2, 4
I I n n
H 13C 6O
O C6H 13
C6H 13O
OC 6H 13
S
S H
n = 2, 4
H
H
H
S
S
OC 6H13 H 13C 6O
H 13C6O
OC 6H 13
n
n
N
H
N N
H
N
n n
H13C 6O
OC 6H 13
C 6H 13O
O C6H 13
S
S H
n = 2, 4
H
H H
I I
3
3
N N
H H
N H H N N
N +
3 H
H
N N
I 3
I
3
H H
Scheme 9. Synthesis of cross-shaped π–conjugated meso-phenyl porphyrin derivatives.
10

11. N
N
H13C6O
OC6H13
C6H13O
OC6H13
S
S
N
OC6H13 H
N N
H
N
N N + N H
N
H
N I S
H13C6O
S
S
H13C6O OC6H13
H13C6O
OC6H13
N N
Scheme 10. Synthesis of π–conjugated meso-phenyl porphyrin bearing peripheral pyridyl.
11

12. Doctoral Synthesis.
O
Cl
HO OH O S Me
OH O MeSO2 Cl, NEt3, O
K2 CO 3 DMAP/CH 2Cl2 O
OH o O O O
DMF, 110 C OH 92.5% yield O S Me
70% yield O
(R)-BINOL (R)-BE (R)-BES
N
Br N N N
LiBr O O -
2 PF6
O O
DMSO 1)MeCN N
Br
50% yield 2)KPF6
(R)-BEB 74% yield (R)-BEBP N
Br
1) DMF (110 oC)
Br
1) MeCN, 110 oC
Br 2) KPF6
2) KPF6 , 11% yield 90% yield
N N
N
O
4x PF 6 N
O O
N 4x PF-6
O
N N
(R)-CBEBPB
N
(R)-BEBPB
Scheme 1. Synthesis of chiroptically switching molecules (R)-BEBPB and (R)-CBEBPB.
C3 H7 Br Br
N N N N
PPB
N
Br Br
Br Br2, CH2 Cl 2 o
Br 1) PPB, DMF (110 C) N
O O O 4 x PF6
O O 2) KPF6 , 80.0 % O
Br Br N
Br Br
(R)-BEB (R)-BBEB (R)-BBEBPP N
12

13. Scheme 2. Synthesis of PPB and (R)-BBEBPP.
Br Br
Cl OH
OH Br 2 HO
OH O
OH CH 2Cl2 OH O
DMF, K2CO3 OH
-78 0C
Br Br
(R)-DBB
Scheme 3. Synthesis of monomer (R)-DBB.
Br
Pd(PPh3 )4, K2CO3 OH
O
OH O O THF/H 2O (v/v, 1/1 )
O O
+ B B HO
O
OH O O 95 oC
C 8H 17 C8H17 n
Br
(R)-DBB P1 C 8H 17 C8 H17
OSO 2Me I
O KI / DMF O
MeSO2Cl, NEt3, DMAP
O 80 o C O
MeO 2SO I
CH 2Cl2
n n
P2 C 8H 17 C8 H17 P3 C 8H 17 C8 H17
Br
N+
N+ I
Br
N N+ O
m
KI / DMF O
o
80 C C 8H17 C 8H 17 I
N+
P4
N+ Br
Scheme 4. Synthetic route for optically active polymers P1, P2, P3 and P4.
13

14. HO NaBrO3 , NaHSO 3 HO SOCl2 Cl
CH 2Br CH 2Br
O CH 3COOC 2 H5 O O
BBC
O
H H
HOOC N OC(CH 3 )3 DCC, DMAP N OC(CH 3 )3
NH2 + N
THF H
CH 3 O CH 3 O
EM1
O
H
1) HCl BBC N
N CH2 Br
CHCl3 , Na2 CO3 /H2 O H
2) Na2 CO 3/H 2O CH 3 O
EM2
N N O
H
Br N
N CH2 N N
H
CH 3OH, 50o C CH 3 O
2Br
EM3
Scheme 5. Synthetic routes of monomers contained terminal acetylene.
O C C n O
H Rh(NBD)[B(C6H5)4 ] H
N H
N CH 2 Br N
H N CH 2 Br
CH3 O THF H
CH3 O
EM2 PEM2
N
Br
N
N
CHCl3
1)
6
PF
K
N Br
2)
C C n O
H H
N H2
15
N C N N
H
CH3 O
-
2 PF 6
PEM4
C C n O
H H
N H2
N C N N
H 15
CH 3 O
2Br
PEM5
Scheme 6. Synthetic routes of polyacetylenes.
14