Synthesis and Characterization of Two Unsymmetrical Indenofluorene Analogues: Benzo[5,6]-s-indaceno[1,2-b]thiophene and Benzo[5,6]-s-indaceno[2,1-b]thiophene

Article abstract of DOI:10.1021/acs.joc.6b00340

The synthesis and characterization of two benzo-indaceno-thiophene compounds (anti-BIT and syn-BIT) are described. Two sequential Suzuki cross-couplings utilizing the halogen selectivity of this reaction permit modular assembly of unsymmetrical indeno[1,2

Full text of DOI:10.1021/acs.joc.6b00340

Subscriber access provided by UNIV OF SOUTHERN QUEENSLAND
Article
Synthesis and Characterization of Two Unsymmetrical
Indenofluorene Analogues: Benzo[5,6]-s-indaceno[1,2-
b]thiophene and Benzo[5,6]-s-indaceno[2,1-b]thiophene
Jonathan L. Marshall, Nathaniel J. O'Neal, Lev N. Zakharov, and Michael M. Haley
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00340 • Publication Date (Web): 25 Mar 2016
Downloaded from http://pubs.acs.org on March 28, 2016
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 23
The Journal of Organic Chemistry
1
2
3
4
Synthesis and Characterization of Two Unsymmetrical Indenofluorene Analogues:
5
6
Benzo[5,6]-s-indaceno[1,2-b]thiophene and Benzo[5,6]-s-indaceno[2,1-b]thiophene
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Jonathan L. Marshall, Nathaniel J. O’Neal, Lev N. Zakharov, and Michael M. Haley*
Department of Chemistry & Biochemistry and Materials Science Institute, University of Oregon,
Eugene, Oregon 97403-1253, United States
E-mail address: haley@uoregon.edu
Abstract: The synthesis and characterization of two benzo-indaceno-thiophene compounds
(anti-BIT and syn-BIT) are described. Two sequential Suzuki cross-couplings utilizing the
halogen selectivity of this reaction permit modular assembly of unsymmetrical indeno[1,2-
b]fluorene analogues. Analysis of their cyclic voltammetry and UV-Vis spectra reveal the optical
and electrochemical properties of the BITs lie between those of indeno[1,2-b]fluorenes and
indacenedithiophenes.
1
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 23
1
2
3
4
Introduction
5
6
7
8
Indenofluorenes (IFs) are an interesting class of cyclopentane-fused hydrocarbons that have
been the focus of interest of our lab,1-14 as well as others,15-26 over the last five years. In addition
to pure hydrocarbon structures such as IFs 1a,b, variants containing thiophene such as
indacenedithiophene (anti-IDT 2a, syn-IDT 3a) or indacenedibenzothiophene (anti-IDBT 2b,
syn-IDBT 3b) and selenophene such as indacenediselenophene (IDS 2c) have also recently been
disclosed (Figure 1).8,13,14,16 Structurally similar to pentacene, the inclusion of two carbonaceous,
fully conjugated five-membered rings such as in 1a-b, 2a-c, or 3a-b impart an intrinsic ability to
accept electrons.1-3,8,14 We have explored both substitution of the IFs at the 2- and 8- positions
(e.g., 1a)2 or 6- and 12-positions (1b)1 with some variations of 1b displaying amphoteric redox
behavior. It should be noted that in all cases for IFs and related structures, the current synthetic
methods for outer ring substitution or core construction limit us to C2h symmetric compounds.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
R1
R2
R2
R1
1a (R1 = CCSi(i-Pr)3, R2 = EWD/EDG)
1b (R1 = Ar, R2 = H)
R2
R2
R2
R2
R1
R1
X
R2
R2
S
S
R1
R1
X
R2
R2
3a (R1 = Mes, R2 = H)
3b (R1 = Ar, R2 = Benzo)
2a (X = S, R1 = Mes, R2 = H)
2b (X = S, R1 = Ar, R2 = Benzo)
2c (X = Se, R1 = Mes, R2 = H)
Figure 1. Indenofluorenes (1a-b) and related heterocyclic congeners (2a-c, 3a-b).
Conjugated polycyclic hydrocarbons have captivated chemists’ imagination over the last two
decades due to their interesting optoelectronic properties and application in organic
electronics.27-40 Research into acenes for use in organic electronics has focused on tuning their
2
ACS Paragon Plus Environment

Page 3 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
optoelectronic properties while at the same time optimizing the solid-state structure to maximize
intermolecular interactions.32,34,41,42 Recently, desymmetrization (breaking the D2v or C2h
symmetry of typical acenes) has been used as a means of creating a dipole moment (4 and 5,
Figure 2) and exploiting this property to influence the solid-state packing. Others have utilized
the desymmetrization of acenes to tune the electronics (5 and 6).43-50 Despite the promise of these
unsymmetrical acenes, their study is fairly limited given their compound specific and often
difficult preparation.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Acene-based unsymmetrical derivatives
F
F
F
F
4
R
N
S
S
N
S
R
6 (R = CCSi(i-Pr)3
5
IF-based unsymmetrical derivatives
Mes
Mes
S
S
Mes
Mes
7a
8a
Figure 2. Unsymmetric acenes 4-6 and unsymmetric IF analogues anti-BIT 7a and syn-BIT 8a.
As the synthesis of IFs and related structures utilizes a Suzuki cross-coupling to attach
various aryl rings to what will eventually become the s-indacene core, we anticipated that the
halogen selectivity of this reaction could be used to desymmetrize IFs in a modular fashion. By
desymmetrizing the IFs, we gain access not only to derivatives which could utilize a dipole to
influence the solid-state packing, but also we access a powerful new strategy to study the
electronic communication through the IF core via donor-acceptor and cruciform topologies. As a
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 23
1
2
3
4
5
6
7
8
9
proof of concept, we have developed a modular synthesis via sequential Suzuki cross-couplings
from diethyl 2-bromo-5-chloroterephthalate 9 for the preparation of new unsymmetrical IF
analogues, benzo[5,6]-s-indaceno[1,2-b]thiophene (anti-BIT 7a-b) and benzo[5,6]-s-
indaceno[2,1-b]thiophene (syn-BIT 8a-c).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Results and Discussion
Symmetric IFs and their congeners are usually prepared by Pd-mediated cross-coupling of
aryl boronic acids to 1,4-dibromo-2,5-dimethylbenzene or diethyl 2,5-dibromoterephthalate.
Intramolecular Friedel-Crafts acylation of the resultant p-terphenyl derivatives provide the
corresponding diones that can be elaborated further into the fully conjugated IF/IDT/IDBT/IDS
via nucleophilic addition of aryl or ethynyl groups followed by a SnCl2-mediated reductive
dearomatization. Utilizing diethyl 2-bromo-5-chloroterephthalate (9, Scheme 1) allows us to
perform sequential and selective Suzuki-Miyaura cross-coupling reactions to attach a variety of
different aryl groups to the IF core. Surprisingly, outside of a few patents, the precursor to 9, 1-
bromo-4-chloro-2,5-dimethylbenzene (10), is poorly represented in the literature.51,52
Bromination of commercially available 2-chloro-1,4-dimethylbenzene (11) furnishes 10, which
in turn is readily converted to terephthalate 9 via KMnO4 oxidation followed by Fischer
esterification to provide the key cross-coupling partner in excellent yield on 15-gram scale. With
9 in hand, standard Suzuki-Miyaura conditions affords biphenyl 12. Switching to the more
activating SPhos ligand permits cross-coupling of either 2- or 3-thienylboronic acid to furnish
diesters 13 or 14, respectively.53 Saponification followed by conversion to the acid chloride and
finally a Friedel-Crafts acylation provides the BIT-diones 15 and 16 in good overall yields on
gram scale. Surprisingly, unlike other IF-diones synthesized in our lab, 15 and 16 were
appreciably soluble in a variety of chlorinated and aromatic solvents. We ascribe this to the
4
ACS Paragon Plus Environment

Page 5 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
unsymmetrical nature of the diones and the slight dipole moment this imparts. Treatment of
dione 15 with mesitylmagnesium bromide followed by SnCl2-mediated reductive
dearomatization in degassed toluene gratifyingly furnished anti-BIT 7a while treatment of dione
16 with mesityllithium (via t-BuLi and bromomesitylene) followed by the SnCl2 reaction
provided syn-BIT 8a.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 1. Synthesis of anti-BITs 7a,b and syn-BITs 8a-c
S
B(OH)2
Pd(PPh3)4
Na2CO3
B(OH)2
Me
Cl
Me
Br
Cl
EtO2C
Br
Cl
EtO2C
Ph
Cl
1. KMnO4
2. H2SO4, EtOH
Pd(OAc)2
SPhos, K3PO4
Br2, I2
83%
93%
75%
Me
CO2Et
Me
CO2Et
11
10
9
12
S
O
O
1. KOH, EtOH
H2O
EtO2C
OR
S
2. (COCl)2, DMF
3. AlCl3
S
O
O
Ph
CO2Et
15 (72%)
16 (77%)
13 (2-thienyl, 50%)
14 (3-thienyl, 85%)
1. MesMgBr
2. H3O+
3. SnCl2
38%
1. MesBr, BuLi
2. H3O+
3. SnCl2
33%
1. MesBr, t-BuLi
2. H3O+
3. SnCl2
1. MesMgBr
2. H3O+
3. SnCl2
14%
Mes
Mes
S
Mes
S
Mes
S
S
Mes
Mes
Mes
Mes
Bu
R
7a
7b
8a
8b (R = Mes, 39%)
8c (R = 8a, < 1%)
Surprisingly, both diones 15 and 16 showed unexpected reactivity to the nucleophilic source
used. Treatment of 15 with mesityllithium (via n-BuLi and bromomesitylene) did not yield anti-
BIT 7a, but rather anti-BIT 7b (see SI for crystal structure of 7b). We believe that mesityllithium
was sufficient to deprotonate the dione (or some intermediate structure) at the α-position of the
thiophene ring and that this deprotonated species reacted with 1-bromobutane (produced by the
lithium-halogen exchange with bromomesitylene) to eventually yield the butylated anti-BIT 7b.
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 23
1
2
3
4
5
6
7
8
9
Similarly, treatment of 16 with mesityllithium (via n-BuLi and bromomesitylene) yielded an
inseparable mixture of 8a and the corresponding butylated product. Much to our surprise,
treatment of 16 with mesitylmagnesium bromide did not furnish 8a; rather, compound 8b and
trace amounts of BIT dimer 8c were isolated. Although Grignard-mediated couplings of
thiophenes are known,54-56 the formation of 8b and 8c was nonetheless an unexpected result
based on the lack of anomalous reactivity of 15 and the dione precursors of 2a-c and 3a-b to
Grignard reagents. By preparing the mesityllithium reagent with t-BuLi, we were able to
suppress the SN2 reaction of any deprotonated dione and isolate pure 8a albeit in reduced yield
compared with 7a.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 3. Electronic absorption spectra of BIT diones 15 and 16 (top) and of IF 1b (R1 = Mes, R2 = H),
anti-BIT 7a, syn-BIT 8a, anti-IDT 2a, and syn-IDT 3a (bottom).
6
ACS Paragon Plus Environment

Page 7 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Figure 3 shows the electronic absorption spectra for diones 15 and 16 (top) and BITs 7a and
8a (bottom). These data along with the experimentally determined Eredox values, HOMO and
LUMO energies and energy gaps are summarized in Table 1. The spectra of diones 15 and 16
show strong absorptions from 275-325 nm with broad absorptions attributable to weak π→π*
transitions in the 450-600 nm range. The spectra of both fully conjugated BITs 7a and 8a show a
maximum absorbance from 275-350 nm and a lower energy λmax of 532 nm for 7a and a λmax of
543 nm for 8a. Surprisingly, syn-BIT 8a shows a weak tail out to 925 nm. The absorbance
profiles of the BITs lie halfway between IF 1b and the corresponding syn- or anti-IDT 2a or 3a,
and as with all previous IFs and IDTs, BITs 7a and 8a are non-emissive.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 1. Electrochemical and Optical Data for BIT Diones 15 and 16 and BITs 7a and 8a.
Electrochemical a
Optical b
1
2
1
2
Ered
(V)
Ered
(V)
Eox
Eox
EHOMO ELUMO Egap
λmax λonset Egap
(nm) (nm) (eV)
compd
(V)
(V)
(eV)
(eV)
(eV)
15
−0.86 −1.29
—
—
—
−3.78
—
525 619
510 610
532 562
543 572
2.00
2.03
2.21
2.16
16
7a
8a
−0.83 −1.24
—
—
—
−3.81
—
−1.06 −1.77c 0.99 1.61c −5.63 −3.58 2.05
−1.04 −1.68c 0.89
−5.53 −3.60 1.93
—
a Spectra were obtained in CH2Cl2. The optical HOMO/LUMO gap was determined as the intersection of the x-axis
and a tangent line passing through the inflection point of the lowest energy absorption. b CVs were recorded using 1-
5 mM of analyte in 0.1 M Bu4NBF4/CH2Cl2 at a scan rate of 50 mV s–1 with a glassy carbon working electrode, a Pt
coil counter electrode, and a Ag wire pseudo-reference. Values reported as the half-wave potential (vs. SCE) using
the Fc/Fc+ couple (0.46 V) as an internal standard. HOMO and LUMO energy levels in eV were approximated using
c
SCE = –4.68 eV vs. vacuum and E1/2 values for reversible processes or Ep values for irreversible processes.
Reported as V at peak current, not half-wave potential.
Both anti-BIT 7a and syn-BIT 8a undergo one reversible reduction in the solution state with
the second reduction being irreversible (Figure 4). The first oxidations of 7a and 8a were quasi-
reversible and fully reversible, respectively, while the second oxidation of 8a was quasi-
reversible. For both 7a and 8a, when the current is swept through the second reduction, a new
peak appears during the cathodic sweep of the CV scan (see Figures S1-S2 in the SI). This peak
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 23
1
2
3
4
5
6
7
8
9
is absent when the current is not swept past the first reduction, indicating that this peak most
likely arises from the reactive species created during the second reduction of 7a and 8a. As seen
with the UV/vis spectra, the electrochemical behavior of the BITs lies in between the IFs and
IDTs. While the ELUMO of IF 1b, anti-BIT 7a, and syn-BIT 8a are nearly the same (–3.56, –3.58,
–3.60 eV, respectively), the EHOMO of 7a and 8a are stabilized when compared with IF 1b. The
resultant Egap of BITs 7a and 8a (2.05 and 1.93 eV, respectively) lies in between the Egap of IF
1b (2.22 eV) and IDTs 2a and 3a (1.88 and 1.85 eV, respectively).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 4. Cyclic voltammogram of anti-BIT 7a and syn-BIT 8a.
Single crystals of 15, 7a,b and 8a,b suitable for x-ray diffraction (XRD) were grown by slow
diffusion of CH3CN into a solution of CH2Cl2 while single crystals of 8c were grown by the slow
evaporation of hexanes. The structures of 7a, 8a, and 8c are shown in Figure 5 (see SI for 15, 7b
and 8b). The crystal structures of 7a and 8a showed disorder over two centro-symmetrical
positions corresponding two opposite orientations, indicating that the dipole induced by
desymmetrization was insufficient to direct the solid-state ordering of these compounds. A
comparison of select bond lengths of the BITs (7a, 8a) along with the dimesityl derivative of
[1,2-b]IF 1b and IDTs 2a and 3a are given in Table 2 (see Table S1 in SI for select bond lengths
of 7b, and 8b,c). All derivatives of 7 and 8 showed bond length alternation of the s-indacene core
8
ACS Paragon Plus Environment

Page 9 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 5. Molecular structures of 7a, 8a, and 8c; hydrogen atoms omitted for clarity. Ellipsoids drawn at
50% probability level.
Table 2. Selected Bond Lengths (Å) For 7a, 8a, 1b, 2a, and 3a
anti/syn-BIT
IF, anti/syn-IDTb
bonda
C1–C2
C2–C3
C3–C4
C4–C5
C5–C6
7a
8a
1b (Mes)
2a
3a
1.468(4)
1.385(3)
1.427(3)
1.359(3)
1.463(4)
1.453(3)
1.388(2)
1.427(2)
1.361(2)
1.467(2)
1.471(3)
1.380(2)
1.433(3)
1.356(2)
1.467(3)
1.460(2)
1.388(2)
1.431(2)
1.360(2)
1.469(2)
1.447(3)
1.398(3)
1.418(3)
1.363(3)
1.456(3)
a Numbering scheme shown in Figure 5. b Numbering scheme for 1b, 2a, and 3a is the
same for 7a and 8a, and shown in Figure S4 of the SI.
indicative of a quinoidal structure. From a bond length perspective, there were no significant
structural differences between the BIT syn/anti isomers nor between indacene cores of the BITs,
IDTs or the dimesityl derivative of IF 1b. The dihedral angle between the average planes of the
9
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 23
1
2
3
4
5
6
7
8
9
mesityl groups and BIT core for 7a (67.4°) and 8a (69.9°) is similar to that of the mesityl
derivative of 1b (68.0°), 2a (67.0°) and 3a (62.2°). Interestingly, the structure of dimer 8c
showedco-planarity of the two BIT cores (0.0° angle between the average planes) while the
thiophene-thiophene bond (C7-C7`) was 1.45 Å, in excellent agreement with the corresponding
bond length reported for various oligothiophene dervatives (~1.44-1.45 Å).57-59 This information
suggests electronic communication between the BIT cores of the dimer; further study is on-going.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 6. Packing diagrams of 7a (a, b) and 8a (c, d); hydrogen atoms and mesityl groups omitted for
clarity.
Both anti-BIT 7a and syn-BIT 8a pack in a herringbone like manner (Figure 6). The sulfur of
7a partakes in a close C–S contact of 3.37Å while the distance between the sulfur and the
average plane of the anti-BIT core is 3.32 Å. Conversely, syn-BIT 8a shows no close C–C or C–
S contacts and the shortest distance between the average plane of the syn-BIT core and the
nearest adjacent molecule is 3.40 Å. syn-BIT dimer 8c packs in an expanded herringbone motif
with no close C–C or C–S contacts and no overlap of the BIT core (see SI).
10
ACS Paragon Plus Environment

Page 11 of 23
The Journal of Organic Chemistry
1
2
3
4
Conclusions
5
6
7
8
In summary, we have developed a modular synthetic route towards the synthesis of
unsymmetric IFs and related compounds. This synthetic route allows us unprecedented
regioselective control and we have demonstrated the synthetic utility of this route by
synthesizing two new unsymmetrical IF analogues, anti-BIT 7a and syn-BIT 8a. Optical and
electrochemical characterization reveals that the BITs properties lie in between that of the IFs
and IDTs. With the synthetic utility of this route clearly demonstrated, we are now using this
methodology to synthesize previously inaccessible IFs possessing strong dipole moments or
cruciform topologies to exploit potential solid-state order or study the electronic nature of the
indenofluorene core.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Experimental Section
General Remarks. All air-sensitive manipulations were carried out under an inert
atmosphere using either standard Schlenk technique or an N2-filled drybox. For air sensitive
reactions, THF and toluene were refluxed with Na benzophenone ketyl for 24 h prior to
distillation and use. For all manipulations performed in a N2-filled drybox, THF and toluene
were refluxed with Na benzophenone ketyl for 24 h prior to distillation and then degassed via
freeze pump thaw cycles. All other reagents were used as received without further purification.
NMR spectra were recorded on a 300 and 500 MHz instrument and a 500 and 600 MHz
1
instrument equipped with a cryoprobe. H and 13C chemical shifts (δ) are expressed in ppm
13
13
relative to the residual CHCl3 (1H: 7.26 ppm, C: 77.16 ppm) and DMSO (1H: 2.50 ppm, C:
39.52 ppm) reference. UV-Vis spectra were recorded on a UV-Vis spectrometer in HPLC grade
CH2Cl2.
11
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 23
1
2
3
4
5
6
7
8
9
1-Bromo-4-chloro-2,5-dimethylbenzene (10). 2-Chloro-1,4-dimethylbenzene (9.44 mL, 71.2
mmol, 1 equiv), iodine (0.091 g, 0.36 mmol, 0.005 equiv) and CH2Cl2 (100 mL) were degassed
with N2 for 15 min and cooled to 0 °C. Bromine (3.85 mL, 74.7 mmol, 1.05 equiv) was added
dropwise and the reaction mixture was stirred for 18 h in the dark while warming to room
temperature. The reaction mixture was quenched with 10% KOH solution, and then extracted
with CH2Cl2 (3×). The combined organic fractions were then washed with brine (3×), dried
(MgSO4), filtered, and concentrated in vacuo. The crude product was recrystallized from EtOH
to yield 10 (12.9 g, 83%) as white crystals. Mp 66-67 °C. 1H NMR (300 MHz, CDCl3) δ 7.38 (s,
1H), 7.20 (s, 1H), 2.33 (s, 3H), 2.31 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 136.8, 135.2, 134.2,
133.2, 130.9, 122.6, 22.4, 19.4. HRMS (TOF MS AP+) for C8H8ClBr: calcd 217.9498, found
217.9510.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Diethyl 2-bromo-5-chloroterephthalate (9). 1-Bromo-4-chloro-2,5-dimethylbenzene 10
(12.77 g, 58.2 mmol, 1 equiv), KMnO4 (20.23 g, 128 mmol, 2.2 equiv), H2O (100 mL) and t-
BuOH (100 mL) were stirred at reflux for 1 h. After cooling, additional KMnO4 (20.23 g, 128
mmol, 2.2 equiv) was added and the mixture was then refluxed for 18 h. After cooling, the
mixture was filtered and the diacid was precipitated by careful addition of conc. HCl solution to
yield 2-bromo-5-chloroterephthalic acid (14.84 g, 91%) as a white powder that was carried on
without further purification. The crude diacid (14.84 g, 52.0 mmol, 1 equiv), conc. H2SO4 (57
mL), and EtOH (400 mL) were stirred at reflux for 18 h. After cooling, EtOH was removed
under reduced pressure. The reaction mixture was partially neutralized by addition of saturated
NaHCO3 solution and then fully neutralized by careful addition of solid KOH pellets. The
precipitate was collected via vacuum filtration and then dissolved in CH2Cl2 to separate the salts
from the product. The solution was dried (MgSO4), filtered, and the solvent was removed under
reduced pressure. Recrystallization of the crude material from EtOH furnished diester 9 (14.22 g,
12
ACS Paragon Plus Environment

Page 13 of 23
The Journal of Organic Chemistry
1
2
3
4
1
82%) as brilliant white crystals. Mp 117-118 °C. H NMR (500 MHz, CDCl3) δ 8.07 (s, 1H),
5
6
7
8
7.83 (s, 1H), 4.41 (q, J = 7.2 Hz, 4H), 1.41 (t, J = 7.2 Hz, 6H). 13C NMR (126 MHz, CDCl3) δ
164.5, 163.8, 136.7, 135.9, 133.7, 133.4, 132.7, 119.3, 62.5, 62.4, 14.29, 14.27. HRMS (TOF
MS FAB+) for C12H13O4ClBr (M+H)+: calcd 334.9686, found 334.9670.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Diethyl 2-chloro-5-phenylterephthalate (12). Diethyl 2-bromo-5-chloroterephthalate 9 (7.00
g, 20.9 mmol, 1 equiv), phenylboronic acid (3.05 g, 25.0 mmol, 1.2 equiv), Na2CO3 (4.42 g, 41.7
mmol, 2 equiv), H2O (30 mL) and toluene (300 mL) were degassed for 60 min with N2.
Pd(PPh3)4 (0.482 g, 0.42 mmol, 0.02 equiv) was then added and the resulting solution was
degassed for a further 10 min. The mixture was then stirred at reflux for 18 h. After cooling, the
mixture was quenched with H2O and extracted with Et2O (3×). The organic layers were
combined, washed with brine (3×), dried (MgSO4), filtered and concentrated in vacuo. The
product was purified via flash chromatography (SiO2, 2:1 CH2Cl2:hexanes) to provide 12 (6.94 g,
1
93%) as clear oil that slowly solidified to a white solid. Mp 55-56 °C. H NMR (500 MHz,
CDCl3) δ 7.88 (s, 1H), 7.80 (s, 1H), 7.43–7.36 (m, 3H), 7.32–7.27 (m, 2H), 4.42 (q, J = 7.1 Hz,
13
2H), 4.11 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H), 1.01 (t, J = 7.2 Hz, 3H). C NMR (126
MHz, CDCl3) δ 166.9, 165.1, 140.9, 139.5, 134.8, 133.4, 132.6, 132.5, 132.1, 128.44, 128.36,
128.0, 62.1, 61.7, 14.3, 13.8. HRMS (TOF MS ES+) for C18H18O4Cl (M+H)+: calcd 333.0894,
found 333.0899.
Diethyl 2-phenyl-5-(2-thienyl)terephthalate (13). An air-free oven dried three-necked round-
bottomed flask fitted with a condenser was charged with diester 12 (3.0 g, 9.01 mmol, 1 equiv),
2-thienylboronic acid (1.38 g, 10.8 mmol, 1.2 equiv), K3PO4, (3.825 g, 18.0 mmol, 2 equiv),
SPhos ligand (0.148 g, 0.36 mmol, 0.04 equiv) and Pd(OAc)2 (0.0405 g, 0.18 mmol, 0.02 equiv).
Dry toluene (125 mL) was added to the flask and N2 was bubbled through the reaction mixture
for 10 min. After refluxing overnight and cooling to room temperature, the reaction mixture was
13
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 23
1
2
3
4
5
6
7
8
9
quenched with H2O and extracted with Et2O (3×). The combined organic layers were then
washed with brine (3×), dried (MgSO4), filtered and concentrated in vacuo. The resultant crude
yellow oil was purified via column chromatography (SiO2, 19:1 hexanes/EtOAc) to yield diester
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
13 (1.70 g, 50%) as a fluffy white solid. Mp 74-75 °C. H NMR (600 MHz, CDCl3) δ 7.92 (s,
1H), 7.72 (s, 1H), 7.43–7.38 (m, 4H), 7.36–7.33 (m, 2H), 7.11 (dd, J = 3.5, 1.3 Hz, 1H), 7.08 (dd,
J = 5.0, 3.6 Hz, 1H), 4.22 (q, J = 7.1 Hz, 2H), 4.11 (q, J = 7.1 Hz, 2H), 1.15 (t, J = 7.1 Hz, 3H),
1.01 (t, J = 7.2 Hz, 3H).13C NMR (151 MHz, CDCl3) δ 168.1, 167.9, 141.8, 140.8, 140.1, 134.4,
133.5, 133.1, 132.4, 131.6, 128.5, 128.3, 127.8, 127.4, 127.0, 126.5, 61.7, 61.5, 14.0, 13.8.
HRMS (TOF MS ES+) for C22H21O4S (M+H)+: calcd 381.1161, found 381.1156.
Diethyl 2-phenyl-5-(3-thienyl)terephthalate (14). The above procedure was followed using 3-
thienylboronic acid instead. Recrystallization of the crude material from EtOH yielded diester 14
1
(2.92 g, 85%) as white needles. Mp 117-118 °C. H NMR (600 MHz, CDCl3) δ 7.85 (s, 1H),
7.76 (s, 1H), 7.45–7.34 (m, 6H), 7.32 (dd, J = 3.0, 1.3 Hz, 1H), 7.14 (dd, J = 4.9, 1.3 Hz, 1H),
4.19 (q, J = 7.1 Hz, 2H), 4.11 (q, J = 7.1 Hz, 2H), 1.14 (t, J = 7.1 Hz, 3H), 1.00 (t, J = 7.1 Hz,
3H). 13C NMR (151 MHz, CDCl3) δ 168.2, 168.1, 141.3, 140.29, 140.28, 135.6, 133.71, 133.66,
131.8, 131.7, 128.53, 128.51, 128.3, 127.7, 125.5, 123.0, 61.6, 61.5, 14.0, 13.8. HRMS (TOF
MS ES+) for C22H21O4S (M+H)+: calcd 381.1161, found 381.1178.
General Procedure for Dione Synthesis. Diester (1 equiv) and KOH (16 equiv) were
refluxed in a 4:1 mixture of EtOH and H2O (0.03 M) for 18 h. The EtOH was removed under
reduced pressure and after cooling to 0 °C, the diacid was precipitated by careful addition of
conc. HCl solution. The solid was collected by filtration, washed with water and dried. The crude
diacid was carried on without further characterization. To a stirred suspension of crude diacid (1
equiv) and oxalyl chloride (4 equiv) in dry CH2Cl2 (0.04 M) at 0 °C under a N2 atmosphere in an
oven-dried flask, DMF (2 equiv) was added dropwise. The reaction mixture was warmed slowly
14
ACS Paragon Plus Environment

Page 15 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
to room temperature with stirring over 6 h, and then was evaporated to dryness under reduced
pressure. The crude acid chloride was re-dissolved in dry CH2Cl2 (0.08 M) and cooled to 0 °C
under N2. A 0 °C solution of AlCl3 (2.62 g, 19.65 mmol, 5 equiv) in dry CH2Cl2 (0.4 M) was
transferred to the crude acid chloride solution via cannula and the resulting mixture was warmed
to room temperature overnight with stirring. This solution was then poured into an HCl/ice
mixture and the resulting dione was collected via vacuum filtration, washed with H2O, EtOH,
hexanes, acetone, and then oven dried at 70 °C.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Anti-Dione 15. Cerulean blue solid (0.871 g, 72% over 3 steps). Mp 334-335 °C, 330 °C
1
(sub). H NMR (500 MHz, CDCl3) δ 7.65 (d, J = 7.5 Hz, 1H), 7.63 (s, 1H), 7.56–7.48 (m, 2H),
13
7.42 (s, 1H), 7.33 (t, J = 7.2 Hz, 1H), 7.24 (d, J = 5.2 Hz, 1H), 7.17 (d, J = 5.0 Hz, 1H). C
NMR (126 MHz, CDCl3) δ 192.8, 186.0, 158.6, 146.3, 143.6, 142.2, 142.0, 139.9, 138.6, 135.4,
133.8, 130.1, 129.6, 124.6, 121.8, 120.6, 115.9, 114.9. UV-Vis (CH2Cl2) λmax (ε) 284 (58100),
290 (93900), 525 (850) nm. HRMS (TOF MS AP-) for C18H8O2S: calcd 288.0245, found
288.0230.
1
Syn-Dione 16. Cerulean blue solid (1.599 g, 77% over 3 steps). Mp 325-326 °C. H NMR
(500 MHz, CDCl3) δ 7.84 (d, J = 4.5 Hz, 1H), 7.70–7.63 (m, 2H), 7.56–7.49 (m, 2H), 7.47 (s,
13
1H), 7.33 (t, J = 7.2 Hz, 1H), 7.18 (d, J = 4.5 Hz, 1H). C NMR (151 MHz, CDCl3) δ 193.1,
184.3, 158.2, 146.0, 143.7, 143.6, 140.9, 140.6, 138.4, 137.0, 135.4, 133.8, 129.5, 124.6, 120.6,
120.5, 116.3, 115.2. UV-Vis (CH2Cl2) λmax (ε) 281 (63900), 284 (84900), 510 (430) nm. HRMS
(TOF MS AP-) for C18H8O2S: calcd 288.0245, found 288.0254.
General Procedure for BIT Synthesis. To a stirred suspension of dione (1 equiv) in THF
(0.01 M) at 0 °C under a N2 atmosphere, mesitylmagnesium bromide (1.0 M in THF, 6 equiv)
was added dropwise. The mixture was then slowly warmed to rt with stirring overnight. The
reaction was quenched with a saturated NH4Cl solution and then extracted with Et2O (3×). The
15
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 23
1
2
3
4
5
6
7
8
9
combined organic fractions were then washed with brine (3×), dried (MgSO4), filtered and then
concentrated in vacuo to provide the crude diol that was carried on without further purification.
In an oven-dried flask in a N2 drybox, the crude diol (1 equiv) was dissolved in dry, degassed
toluene (0.02 M) and vigorously stirred with anhydrous SnCl2 (4 equiv) for 14 h. The reaction
mixture was then filtered through a short plug of silica gel (CH2Cl2). After removing the solvent
in vacuo, the crude product was purified via flash chromatography (SiO2, 4:1 hexanes/CH2Cl2) to
yield the desired BIT.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
anti-BIT 7a. Deep purple solid (324 mg, 38%). Mp 342-343 °C, 337 °C (sub). 1H NMR (600
MHz, CDCl3) δ 7.13 (d, J = 7.2 Hz, 1H), 6.99 (s, 2H), 6.98 (s, 2H), 6.93–6.89 (m, 2H), 6.82 (td,
J = 7.4, 1.1 Hz, 1H), 6.58 (d, J = 7.6 Hz, 1H), 6.52 (s, 1H), 6.47 (s, 1H), 6.38 (d, J = 4.8 Hz, 1H),
2.37 (s, 3H), 2.37 (s, 3H), 2.27 (s, 6H), 2.18 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 151.9, 148.4,
144.0, 142.0, 139.21, 139.17, 137.8, 137.6, 137.1, 137.0, 136.1, 136.0, 135.9, 135.1, 130.7, 129.9,
128.4, 128.3, 127.9, 127.8, 127.3, 122.5, 121.2, 120.6, 120.3, 120.1, 21.32, 21.31, 20.7, 20.6.
UV-Vis (CH2Cl2) λmax (ε) 318 (44700), 327 (47500), 504 (17550), 532 (20000)nm. HRMS (TOF
MS ES+) for C36H31S (M+H)+: calcd 495.2133, found 495.2146.
anti-BIT 7b. An oven-dried flask charged with bromomesitylene (0.63 mL, 4.14 mmol, 6
equiv) and dry THF (25 mL) under N2 was cooled to –78 °C and BuLi (1.6 M in hexanes, 2.16
mL, 3.45 mmol, 5 equiv) was added dropwise. After stirring at –78 °C for 1 h, the mixture was
transferred via cannula to an oven-dried flask changed with dione 15 (200 mg, 0.69 mmol, 1
equiv) in THF (25 mL) at 0 °C under a N2 atmosphere. The mixture was stirred while slowly
warming to room temperature. After 3 d, the reaction was worked up following the general
procedure. Treatment of the crude diol following the general procedure furnished pure anti-BIT
7b (125 mg, 33%) as bright purple crystals. Mp 248-249 °C. 1H NMR (600 MHz, CDCl3) δ 7.08
(d, J = 7.3 Hz, 1H), 6.98 (s, 2H), 6.97 (s, 2H), 6.88 (d, J = 7.7 Hz, 1H), 6.79 (d, J = 7.7 Hz, 1H),
16
ACS Paragon Plus Environment

Page 17 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
6.54 (d, J = 7.5 Hz, 1H), 6.45 (s, 1H), 6.34 (s, 1H), 6.08 (s, 1H), 2.61 (t, J = 7.6 Hz, 2H), 2.37 (s,
3H), 2.36 (s, 3H), 2.27 (s, 6H), 2.18 (s, 6H), 1.59–1.51 (m, 2H), 1.33 (sext, J = 7.4 Hz, 2H), 0.88
7
8
9
13
(t, J = 7.4 Hz, 3H). C NMR (151 MHz, CDCl3) δ 151.5, 149.6, 147.9, 144.1, 142.5, 139.3,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
137.7, 137.5, 137.1, 137.0, 136.8, 136.7, 135.5, 135.4, 135.3, 130.8, 130.0, 128.34, 128.27,
127.8, 127.1, 122.4, 120.5, 120.3, 119.9, 117.8, 33.5, 30.5, 22.2, 21.3, 20.7, 20.6, 13.93. UV-Vis
(CH2Cl2) λmax (ε) 331 (51100), 506 (19900), 536 (21800) nm. HRMS (TOF MS ES+) for C40H39S
(M+H)+: calcd 551.2772, found 551.2765.
syn-BIT 8a. An oven-dried flask charged with bromomesitylene (0.40 mL, 2.6 mmol, 5
equiv) and dry THF (25 mL) under N2 was cooled to –78 °C and t-BuLi (1.7 M in hexanes, 1.84
mL, 3.1 mmol, 6 equiv) was added dropwise. After stir at –78 °C for 1 h, the mixture was
transferred via cannula to an oven-dried flask changed with dione 16 (150 mg, 0.52 mmol, 1
equiv) in THF (25 mL) at –78 °C under a N2 atmosphere. The mixture was stirred while slowly
warmed to room temperature overnight. The reaction was worked up following the general
procedure. Treatment of the crude diol following the general procedure furnished pure syn-BIT
1
8a (34.7 mg, 14%) as a deep purple solid. Mp 335-336 °C, 323 °C (sub). H NMR (600 MHz,
CDCl3) δ 7.13 (d, J = 7.3 Hz, 1H), 7.02 (s, 2H), 7.01 (s, 2H), 6.98 (d, J = 4.8 Hz, 1H), 6.92 (td, J
= 7.4, 1.0 Hz, 1H), 6.85–6.80 (m, 2H), 6.59 (d, J = 7.3 Hz, 1H), 6.534 (s, 1H), 6.528 (s, 1H),
2.40 (s, 3H), 2.39 (s, 3H), 2.33 (s, 6H), 2.21 (s, 6H). 13C NMR (151 MHz, CDCl3) δ 148.7, 148.0,
143.82, 143.78, 141.1, 139.0, 137.8, 137.6, 137.0, 136.9, 136.1, 135.8, 135.2, 135.0, 129.93,
129.87, 128.6, 128.3, 128.1, 127.8, 127.1, 122.4, 121.5, 120.10, 120.05, 119.96, 21.2, 20.5, 20.41.
UV-Vis (CH2Cl2) λmax (ε) 308 (45100), 316 (46100), 510 (21000), 543 (25500) nm. HRMS
(TOF MS ES+) for C36H31S (M+H)+: calcd 495.2146, found 495.2172.
17
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 23
1
2
3
4
5
6
7
8
9
syn-BIT 8b and syn-BIT dimer 8c. Following the general procedure, dione 16 yielded a
mixture of 8b and 8c. Column chromatography (SiO2, 6:1 hexanes/CH2Cl2) afforded pure
material, with 8b eluting first and 8c eluting second. 8b: maroon solid (99.3 mg, 39%). Mp 220-
222°C. 1H NMR (600 MHz, CDCl3) δ 7.11 (d, J = 7.5 Hz, 1H), 6.98 (s, 4H), 6.92–6.88 (m, 3H),
6.80 (d, J = 7.2 Hz, 1H), 6.56 (d, J = 7.5 Hz, 1H), 6.52–6.49 (m, 3H), 2.36 (s, 12H), 2.29 (s, 3H),
2.21–2.16 (m, 12H). 13C NMR (151 MHz, CDCl3) δ 148.7, 148.0, 145.7, 144.0, 143.9, 141.8,
139.3, 138.4, 138.1, 137.9, 137.7, 137.1, 137.0, 136.7, 135.6, 135.2, 134.5, 131.4, 130.2, 130.1,
128.5, 128.3, 127.9, 127.1, 122.5, 121.8, 120.3, 120.2, 120.0, 21.3, 21.2, 20.9, 20.7, 20.6. UV-
Vis (CH2Cl2) λmax (ε) 310 (43800), 319 (44200), 518 (19300), 551 (22800) nm. HRMS (TOF MS
ES+) for C45H41S (M+H)+: calcd 613.2929, found 613.2900. 8c: dark purple solid (<1.0 mg,
<1%). Mp >340 °C. 1H NMR (500 MHz, THF-d8) δ 7.18 (d, J = 7.5 Hz, 2H), 7.05 (s, 2H), 6.97
(s, 4H), 6.95 (s, 4H), 6.85 (t, J = 7.6 Hz, 2H), 6.76 (t, J = 7.5 Hz, 2H), 6.59 (s, 2H), 6.52 (s, 2H),
6.50 (d, J = 7.8 Hz, 2H), 2.32 (s, 6H), 2.31 (s, 6H), 2.26 (s, 12H), 2.13 (s, 12H). Extremely low
solubility precluded 13C NMR analysis. UV-Vis (CH2Cl2) λmax (ε) 320, 383, 587, 890 (br), 1000
(sh) nm. HRMS (TOF MS ES+) for C72H58S2 (M+H)+: calcd 986.3980, found 986.3989.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI:
10.1021/acs.joc.XXXXXXX.
13
1H and C NMR spectra for all new compounds, CV and X-ray crystallographic
data, and bond length comparison for 7b, 8b, and 8c (PDF)
AUTHOR INFORMATION
18
ACS Paragon Plus Environment

Page 19 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Corresponding Author
* haley@uoregon.edu
Notes
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank the National Science Foundation (CHE-1301485) for support of the research as well as
support in the form of an instrumentation grant (CHE-1427987). HRMS were obtained at the
Mass Spectrometry Facilities and Services Core of the Environmental Health Sciences Center,
Oregon State University, supported by grant #L30-CS00210, National Institute of Environmental
Health Sciences, National Institutes of Health.
References
(1)
(2)
(3)
Chase, D. T.; Fix, A. G.; Kang, S. J.; Rose, B. D.; Weber, C. D.; Zhong, Y.; Zakharov, L.
N.; Lonergan, M. C.; Nuckolls, C.; Haley, M. M. J. Am. Chem. Soc. 2012, 134, 10349-
10352.
Chase, D. T.; Fix, A. G.; Rose, B. D.; Weber, C. D.; Nobusue, S.; Stockwell, C. E.;
Zakharov, L. N.; Lonergan, M. C.; Haley, M. M. Angew. Chem. Int. Ed. 2011, 50, 11103-
11106.
Chase, D. T.; Rose, B. D.; McClintock, S. P.; Zakharov, L. N.; Haley, M. M. Angew.
Chem. Int. Ed. 2011, 50, 1127-1130.
(4)
(5)
Fix, A. G.; Chase, D. T.; Haley, M. M. Top. Curr. Chem. 2014, 349, 159-195.
Fix, A. G.; Deal, P. E.; Vonnegut, C. L.; Rose, B. D.; Zakharov, L. N.; Haley, M. M. Org.
Lett. 2013, 15, 1362-1365.
19
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 23
1
2
3
4
5
6
7
8
9
(6)
(7)
Frederickson, C. K.; Haley, M. M. J. Org. Chem. 2014, 79, 11241-11245.
Marshall, J. L.; Haley, M. M. In Organic Redox Systems: Synthesis, Properties and
Applications; Nishinaga, T., Ed.; Wiley: New York, 2016, pp. 311-358.
Marshall, J. L.; Rudebusch, G. E.; Vonnegut, C. L.; Zakharov, L. N.; Haley, M. M.
Tetrahedron Lett. 2015, 56, 3235-3239.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(8)
(9)
Rose, B. D.; Chase, D. T.; Weber, C. D.; Zakharov, L. N.; Lonergan, M. C.; Haley, M. M.
Org. Lett. 2011, 13, 2106-2109.
(10) Rose, B. D.; Maria, P. J. S.; Fix, A. G.; Vonnegut, C. L.; Zakharov, L. N.; Parkin, S. R.;
Haley, M. M. Beil. J. Org. Chem. 2014, 10, 2122-2130.
(11) Rose, B. D.; Sumner, N. J.; Filatov, A. S.; Peters, S. J.; Zakharov, L. N.; Petrukhina, M.
A.; Haley, M. M. J. Am. Chem. Soc. 2014, 136, 9181-9189.
(12) Rose, B. D.; Vonnegut, C. L.; Zakharov, L. N.; Haley, M. M. Org. Lett. 2012, 14, 2426-
2429.
(13) Rudebusch, G. E.; Fix, A. G.; Henthorn, H. A.; Vonnegut, C. L.; Zakharov, L. N.; Haley,
M. M. Chem. Sci. 2014, 5, 3627-3633.
(14) Young, B. S.; Chase, D. T.; Marshall, J. L.; Vonnegut, C. L.; Zakharov, L. N.; Haley, M.
M. Chem. Sci. 2014, 5, 1008-1014.
(15) Miyoshi, H.; Nobusue, S.; Shimizu, A.; Hisaki, I.; Miyata, M.; Tobe, Y. Chem. Sci. 2014,
5, 163-168.
(16) Shi, X.; Burrezo, P. M.; Lee, S.; Zhang, W.; Zheng, B.; Dai, G.; Chang, J.; Lopez
Navarrete, J. T.; Huang, K.-W.; Kim, D.; Casado, J.; Chi, C. Chem. Sci. 2014, 5, 4490-
4503.
(17) Shimizu, A.; Kishi, R.; Nakano, M.; Shiomi, D.; Sato, K.; Takui, T.; Hisaki, I.; Miyata,
M.; Tobe, Y. Angew. Chem. Int. Ed. 2013, 52, 6076-6079.
20
ACS Paragon Plus Environment

Page 21 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(18) Shimizu, A.; Nobusue, S.; Miyoshi, H.; Tobe, Y. Pure Appl. Chem. 2014, 86, 517-528.
(19) Shimizu, A.; Tobe, Y. Angew. Chem. Int. Ed. 2011, 50, 6906-6910.
(20) Takeda, T.; Inukai, K.; Tahara, K.; Tobe, Y. J. Org. Chem. 2011, 76, 9116-9121.
(21) Tobe, Y. Chem. Rec. 2015, 15, 86-96.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(22) Fukuda, K.; Nagami, T.; Fujiyoshi, J.-y.; Nakano, M. J. Phys. Chem. A 2015, 119, 10620-
10627.
(23) Martinez, I.; Zarate, X.; Schott, E.; Morales-Verdejo, C.; Castillo, F.; Manríquez, J. M.;
Chávez, I. Chem. Phys. Lett. 2015, 636, 31-34.
(24) Rao, M. R.; Desmecht, A.; Perepichka, D. F. Chem.–Eur. J. 2015, 21, 6193-6201.
(25) Sbargoud, K.; Mamada, M.; Marrot, J.; Tokito, S.; Yassar, A.; Frigoli, M. Chem. Sci.
2015, 6, 3402-3409.
(26) Zhang, X.-Y.; Huang, J.-D.; Yu, J.-J.; Li, P.; Zhang, W.-P.; Frauenheim, T. Phys. Chem.
Chem. Phys. 2015, 17, 25463-25470.
(27) Organic Light Emitting Devices: Synthesis, Properties and Applications; Mullen, K.,
Scherf, U. (eds); Wiley-VCH: Weinheim, Germany, 2006.
(28) Carbon-rich Compounds: From Molecules to Materials; Haley, M. M., Tykwinski, R. R.
(eds); Wiley-VCH: Weinheim, Germany, 2006.
(29) Functional Organic Materials; Muller, T. J. J., Bunz, U. H. (eds); Wiley-VCH:
Weinheim, Germany, 2007.
(30) Fullerenes: Principles and Applications; Langa, F., Nierengarten, J. F. (eds); Royal
Society of Chemistry: Cambridge, United Kingdom, 2011.
(31) Fullerenes and Other Carbon-Rich Nanostructures; Nierengarten, J. F. (ed); Springer:
Berlin, Germany, 2014.
(32) Anthony, J. E. Chem. Rev. 2006, 106, 5028-5048.
21
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 23
1
2
3
4
5
6
7
8
9
(33) Anthony, J. E. Angew. Chem. Int. Ed. 2008, 47, 452-483.
(34) Anthony, J. E.; Brooks, J. S.; Eaton, D. L.; Parkin, S. R. J. Am. Chem. Soc. 2001, 123,
9482-9483.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(35) Anthony, J. E.; Facchetti, A.; Heeney, M.; Marder, S. R.; Zhan, X. Adv. Mater. 2010, 22,
3876-3892.
(36) Clar, E.; Polycyclic Hydrocarbons; Academic: London, United Kingdom, 1964.
(37) Dong, H.; Fu, X.; Liu, J.; Wang, Z.; Hu, W. Adv. Mater. 2013, 25, 6158-6183.
(38) Dong, H.; Wang, C.; Hu, W. Chem. Commun. 2010, 46, 5211-5222.
(39) Harvey, R. G.; Polycyclic Aromatic Hydrocarbons; Wiley: New York, United States,
1997.
(40) Miao, Q. Synlett 2012, 326-336.
(41) Anthony, J. E. In Functional Organic Materials:Syntheses, Strategies and Applications;
Muller, T. J. J., Bunz, U. H. F. (Eds.); Wiley-VCH: Weinheim, Germany, 2007, pp. 511-
545.
(42) Anthony, J. E. Nat. Mater. 2014, 13, 773-775.
(43) Lei, T.; Zhou, Y.; Cheng, C.-Y.; Cao, Y.; Peng, Y.; Bian, J.; Pei, J. Org. Lett. 2011, 13,
2642-2645.
(44) Swartz, C. R.; Parkin, S. R.; Bullock, J. E.; Anthony, J. E.; Mayer, A. C.; Malliaras, G. G.
Org. Lett. 2005, 7, 3163-3166.
(45) Tang, M. L.; Okamoto, T.; Bao, Z. J. Am. Chem. Soc. 2006, 128, 16002-16003.
(46) Tang, M. L.; Reichardt, A. D.; Miyaki, N.; Stoltenberg, R. M.; Bao, Z. J. Am. Chem. Soc.
2008, 130, 6064-6065.
(47) Tang, M. L.; Reichardt, A. D.; Okamoto, T.; Miyaki, N.; Bao, Z. Adv. Funct. Mater. 2008,
18, 1579-1585.
22
ACS Paragon Plus Environment

Page 23 of 23
The Journal of Organic Chemistry
1
2
3
4
5
6
(48) Tang, M. L.; Reichardt, A. D.; Siegrist, T.; Mannsfeld, S. C. B.; Bao, Z. Chem. Mater.
2008, 20, 4669-4676.
7
8
9
(49) Tang, M. L.; Reichardt, A. D.; Wei, P.; Bao, Z. J. Am. Chem. Soc. 2009, 131, 5264-5273.
(50) Valiyev, F.; Hu, W.-S.; Chen, H.-Y.; Kuo, M.-Y.; Chao, I.; Tao, Y.-T. Chem. Mater.
2007, 19, 3018-3026.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(51) Willgerodt, C.; Wolfien, R. J. Prakt. Chem. 1889, 39, 402-412.
(52) Varma, P. S.; Rman, K. S. V. J. Indian Chem. Soc. 1935, 12, 245-248.
(53) No attempt was made to optimize the Suzuki reactions as the literatures precedents
worked as described..
(54) Cahiez, G.; Duplais, C.; Buendia, J. Angew. Chem. Int. Ed. 2009, 48, 6731-6734.
(55) Cunningham, D. D.; Laguren-Davidson, L.; Mark, H. B.; Van Pham, C.; Zimmer, H. J.
Chem. Soc., Chem. Commun. 1987, 1021.
(56) Moglie, Y.; Mascaró, E.; Nador, F.; Vitale, C.; Radivoy, G. Synth. Commun. 2008, 38,
3861-3874.
(57) Casado, J.; Hernández, V.; Hotta, S.; López Navarrete, J. T. J. Chem. Phys. 1998, 109,
10419.
(58) Chaloner, P. A.; Gunatunga, S. R.; Hitchcock, P. B. Acta Crystallogr. Sect. C: Cryst.
Struct. Commun. 1994, 50, 1941-1942.
(59) Pelletier, M.; Brisse, F. Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 1994, 50,
1942-1945.
23
ACS Paragon Plus Environment