Synthesis and Application of Substituted 1,16-Dihydroxytetraphenylenes in Catalytic Asymmetric Allylboration of Ketones

Article abstract of DOI:10.1021/acs.joc.8b02475

The synthesis and application of a newly designed C₂-symmetric chiral-substituted 1,16-dihedroxytetraphenylene (DHTP) is reported. Efficient syntheses of enantiopure substituted DHTP were accomplished, and these enantiopure compounds were used as organocatalysts in asymmetric allylboration of ketones under very mild conditions. Accordingly, several tertiary alcohols were generated in moderate to good yields with up to 99% ee by using the catalyst (S)-2,15-Br₂-DHTP. A gram-scale reaction was achieved in 99% yield with 96% ee.

Full text of DOI:10.1021/acs.joc.8b02475

Subscriber access provided by Gothenburg University Library
Article
Synthesis and Application of Substituted-1,16-dihydroxytetraphenylenes
in Catalytic Asymmetric Allylboration of Ketones
Guo-Li Chai, Bo Zhu, and Junbiao Chang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02475 • Publication Date (Web): 10 Dec 2018
Downloaded from http://pubs.acs.org on December 12, 2018
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 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 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.
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 29
The Journal of Organic Chemistry
1
2
3
4
5
Synthesis and Application of
6
7
8
9
Substituted-1,16-dihydroxytetraphenylenes in
Catalytic Asymmetric Allylboration of Ketones
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
Guo-Li Chai, Bo Zhu, and Junbiao Chang*
Address: Henan Key Laboratory of Organic Functional Molecules and Drug Innovation,
Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine
Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University,
Xinxiang, Henan 453007, China
Email: Junbiao Chang – changjunbiao@zzu.edu.cn
* Corresponding author
Abstract
The synthesis and application of a newly designed C2-symmetric chiral
substituted-1,16-dihedroxytetraphenylenes (DHTP) is reported. Efficient syntheses of
enantiopure substituted-DHTP were accomplished, and these enantiopure
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 29
1
2
3
4
5
6
compounds were used as organocatalysts in asymmetric allylboration of ketones
under very mild conditions. Accordingly, several tertiary alcohols were generated in
7
8
9
moderate to good yields with up to 99% ee by using the catalyst (S)-2,15-Br2-DHTP.
gram-scale reaction was achieved in 99% yield with 96% ee.
A
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
Introduction
The development of novel chiral catalysts has become a very important task
in the catalytic asymmetric reactions.1 Asymmetric organocatalysis has
attracted wide interest over the past two decades, especially due to its
advantages of environmentally benign, non-toxic nature, and the easy structural
modification of organocatalysts' scaffolds.2 Organocatalysts derived from chiral
biphenols are becoming increasingly versatile catalysts, and have been applied
to catalyze a lot of asymmetric transformations.3 Tetraphenylene with a distinct
saddle-shaped framework was proved to be a non-planar molecule.4 The stable
and rigid backbone of tetraphenylene has been verified to be a new type of
chiral ligands in asymmetric catalysis.5 However, the limited structure diversity
of tetraphenylene, partly due to the lack of effective synthetic method, often
hinders their application.
We now report the synthesis of a new C2-symmetry chiral 2,15-substituted
and 4,13-substituted 1,16-dihydroxytetraphenylene (DHTP) that shows
significantly influence on the catalytic activity by adjusting both the steric and
electronic properties with different substituents. We next explored their
ACS Paragon Plus Environment

Page 3 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
application in the asymmetric allylboration of ketones. These reactions proceed
smoothly under mild reaction conditions with moderate to excellent
enantioselectivities (57-99% ee), as can be seen in Scheme 1.
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. Catalyst 1-Catalyzed Asymmetric Allylboration of Ketones
Results and Discussion
Intrigued by the results of 3,3'-substituted BINOLs, we envisioned that by
introducing electron-withdrawing groups or bulky groups at the 2,15-positions or
4,13-positions of (S)-DHTP (5), we might be able to improve the catalyst reactivity for
asymmetric reactions. As illustrated in Scheme 2, the synthesis of enantiopure
(S)-substituted-DHTP (1, 6, 7, and 10) started from 5. (S)-2,15-Cl2-DHTP 6 was
prepared in 70% yield by chlorination of 5 according to the reported procedures
(Scheme 2, eq 1).6 The bromination of 5 with N-bromosuccinimide (NBS) in DCM at
0 °C gave the (S)-2,15-Br2-DHTP 1 in 71% yield with high regioselectivity. Then, the
Pd-catalyzed cross-coupling reaction of 1 with phenylboronic acid afforded
(S)-2,15-Ph2-DHTP 7 in 90% yield (Scheme 2, eq 2). In addition, this method could
offer an easy access to the disubstituted 2,15-aryl-DHTP. Compound 8 was obtained
in nearly quantitative yield by methylation of 5 with iodomethane. Subsequent
bomination of 8 with NBS in MeCN at room temperature afforded compound 9 in
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 29
1
2
3
4
5
6
7
8
9
quantitative yield with excellent regioselectivity, which was allowed to undergo
demethylation with boron tribromide (BBr3) to furnish the desired product
(S)-4,13-Br2-DHTP 10 in quantitative yield (Scheme 2, eq 3). Starting from
compounds 1 and 10, coupling reactions using different boronic acids could give a
series of chiral aryl-substituted DHTP following the aforementioned protocol. At the
same time, (±)-2,15-Br2-DHTP and (±)-4,13-Br2-DHTP were readily prepared from
(±)-DHTP, making use of the method as described above. The relative configuration of
(±)-2,15-Br2-DHTP (CCDC 1880573) and (±)-4,13-Br2-DHTP (CCDC 1880574) were
determined by X-ray crystallographic analyses (see the Supporting Information for the
relative configuration assignments).
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 2. Synthesis of Substituted-DHTP Catalysts
ACS Paragon Plus Environment

Page 5 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
With the new chiral catalysts in hand, we next evaluated the enantioselective
allylation of ketones. Asymmetric allylboration of carbonyl compounds using Lewis
and Brønsted acid catalysts is an efficient method to synthesize chiral tertiary
homoallylic alcohols.7 Hoveyda reported a class of easily modifiable aminophenol
catalysts that could catalyze asymmetric allylation of imines and carbonyls.8 Research
groups of Chong,9 Schaus,10 Senanayake,11 and Szabó12 employed BINOL derivatives
for enantioselective allylboration. In particular, Schaus et al. reported the asymmetric
allylboration of ketones with acyclic10a or cyclic10b allylboronates using
(S)-3,3'-Br2-BINOL as the most effective catalyst through a crucial ligand exchange
step10c, and all electron-rich and electron-deficient aromatic ketones and
heteroaromatic ketones proceeded with good results. Inspired by their work, we
proceeded to explore the asymmetric allylboration of acetophenone 2a and
B-allyl-1,3,2-dioxaboriane 3 as a model reaction in dry toluene at room temperature
by using 10 mol% chiral tetraphenylene derivatives 5, 6, 1, 7, 10, and (S,S)-THTP 11
as catalysts (Table 1). Our results indicated that the use of 11 and 5 gave only low
yields (33%-54%) and very poor enantioselectivities (Table 1, entries 1 and 2). To our
delight, when the catalyst was replaced by 6, the model reaction proceeded smoothly
to afford the desired product 4a with 88% ee and in 54% yield, indicating that
2,15-substituents have considerable impact on the stereselectivity (Table 1, entry 3).
Furthermore, investigation of the substituent effect of the catalysts disclosed that the
catalyst bearing two Br group at 2,15-position was the most optimal catalyst in terms
of both reactivity and enantioselectivity (Table 1, entries 4-6). With 10 mol% of 1, the
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
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 29
1
2
3
4
5
6
7
8
9
corresponding product 4a was generated in 91% yield and 94% ee (Table 1, entries 4).
When the reaction was carried out in 1 mL toluene, the yield and enantioselectivity
dropped slightly (Table 1, entry 7 vs entry 4).
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. Optimization of the Reaction Conditionsa
entry
Cat*
solvent
time (h)
yieldb (%)
eec (%)
1
2
11
5
toluene
toluene
toluene
toluene
toluene
toluene
toluene
DCM
48
48
48
48
48
24
62
30
24
20
48
33
54
54
91
62
25
67
92
16
33
75
7
8
3
6
88
94
53
50
88
88
34
32
92
4
1
5
7
6
10
1
7d
8
1
9
1
THF
10
11
1
MeCN
o-xylene
1
ACS Paragon Plus Environment

Page 7 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
12
13
1
1
1
1
1
1
PhCl
48
48
48
72
48
48
71
79
92
86
86
69
89
97
98
97
93
93
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
14e
15e,f
16e,g
17e,h
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
R-2,15-Br2
18e,i
PhCF3
48
97
-96
-DHTP
aUnless otherwise stated, all reactions were carried out with 2a (0.1 mmol),
B-allyl-1,3,2-dioxaboriane 3 (0.2 mmol), catalyst (0.01 mmol), t-BuOH (0.2 mmol), and
dry solvent (0.5 mL) being stirred at 25 °C under N2 atmosphere. bIsolated yield. cThe
ee values were determined by chiral HPLC. dWith toluene (1.0 mL). With t-BuOH
e
f
o
g
o
h
i
(0.15 mmol). At 0 C. At 40 C. With 5 mol% catalyst 1 as catalyst. With 10 mol%
R-2,15-Br2-DHTP as catalyst.
Further screening of solvents indicated that the reaction media had a
remarkable impact on the catalytic effects (Table 1, entries 8-13). Chlorinated
solvents such as dichloromethane led to a slightly decreased enantioselectivity
(Table 1, entry 8). Both the yield and selectivity were decreased significantly
when a polar solvent such as THF or MeCN was used (Table 1, entries 9 and
10). Nonpolar solvents such as PhCF3, PhCl and o-xylene appeared to be
beneficial (Table 1, entries 11-13), and PhCF3 was the best solvent for the
reaction. An improved yield was obtained when 1.5 equiv. of t-BuOH was
employed, and the reaction was achieved in 92% yield with 98% ee (Table 1,
entry 14). Meanwhile, varying the reaction temperature with catalyst
1 did not
improve the yield and selectivity (Table 1, entries 15 and 16). When the catalyst
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 29
1
2
3
4
5
loading was decreased to 5 mol%, the desired product was obtained in 69%
6
7
yield with 93% ee (Table 1, entry 17). Fortunately, catalyst
1 could be easily
8
9
recovered in 90% yield by means of flash chromatography after the reaction
，
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
and could be reused without any loss in activity. Meanwhile, the opposite
enantiomer of (S)-4a was formed in 97% yield with -96% ee using
R-2,15-Br2-DHTP as the chiral catalyst (Table 1, entry 18). Thus, the optimized
experimental conditions were as follows: 10 mol%
toluene (0.2 M) at 25 °C. Fortunately, catalyst could be easily recovered in 90%
and could be reused
1 and 1.5 equiv. t-BuOH in
1
yield by means of flash chromatography after the reaction
without any loss in activity.
，
With the optimal reaction conditions in hand, the substrate scope of this
asymmetric reaction was investigated and the results were summarized in
Scheme 3. Reaction of acetophenone 2b with
3 afforded product 4b in 94%
yield with >99% ee (Scheme 3, 4b). Aryl-substituted ketones, including those
with an electron-withdrawing (Scheme 3, 2a, 2c, 2d, and 2e) or
electron-donating (Scheme 3, 2g and 2h) substituent undergo efficient
enantioselective addition. The para- and meta-substituted aryl ketones were
suitable for the reaction, affording the corresponding products in good yields
(82-94%) with excellent enantioselectivities (91-99% ee) (Scheme 3, 4a
4e 4g, and 4h), but the catalytic system was sensitive to the steric bulk of the
substrates, specifically ortho-substituted ketone 2f and 1-naphthyl ketone 2j
, 4c, 4d,
,
,
leading to dramatically diminished yields and enantioselectivities (Scheme 3, 4f
and 4j). In addition, ring-fused naphthyl ketone 2i and heteroaromatic
ACS Paragon Plus Environment

Page 9 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
thiophene ketone 2k could also afford their corresponding products with
moderate to good yield and moderate to excellent enantioselectivities (Scheme
3, 4i and 4k). To our delight, aryl ketones that contain a larger alkyl unit
(Scheme 3, 2l and 2m), cyclic ketones (Scheme 3, 2n and 2o) were also
tolerated in the reaction system, giving desired products with 79-93% yield and
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
91-98% ee. The substrate 2p reacted smoothly with
product 4p in 96% yield and 98% ee (Scheme 3, 4p). In asymmetric
allylbortaion of ketones, our designed catalyst ((S)-2,15-Br2-DHTP) did not
3 to generate the desired
1
achieve better results than 3,3’-Br2-BINOL which was reported by Schaus'
group.10b But in some cases, (S)-2,15-Br2-DHTP shows similar catalytic activity
as 3,3’-Br2-BINOL in asymmetric allylboration reactions (product 4a and 4b),
and it is a useful alternative to the corresponding BINOL catalysts. Furthermore,
products from aryl ketones that contain an alkenyl group were formed with
moderate results (Scheme 3, 4q 90% yield, 61% ee and 4r 24% yield, 74% ee),
and similar results were achieved when additional catalyst was used (Scheme 3,
4q 90% yield, 62% ee and 4r 24% yield, 75% ee). The absolute configuration of
all the products was determined by comparison with literature data.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 29
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
Scheme 3. Substrate Scope in the Catalytic Asymmetric Allylboration of Ketonesa,b,c
aUnless otherwise noted, all reactions were carried out with ketone 2a-r (0.1
mmol), B-allyl-1,3,2-dioxaboriane
3 (0.2 mmol), catalyst 1 (0.01 mmol), t-BuOH
(0.15 mmol), and dry PhCF3 (0.5 mL) being stirred at 25 °C under N2
ACS Paragon Plus Environment

Page 11 of 29
The Journal of Organic Chemistry
1
2
3
4
5
b
c
atmosphere for 48 h-72 h. Isolated yield. The ee values were determined by
6
7
chiral HPLC. dWith 0.02 mmol catalyst
1.
8
9
To demonstrate the synthetic utility of our reaction, a gram-scale allylboration of
acetophenone 2a was performed under standard conditions. Thus,1.44 g of 4a
was obtained with a similar yield and enantioselectivity (Scheme 4), indicating
that the present methodology is amenable to large scale synthesis.
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 4. Gram-scale reaction
Conclusion
In conclusion, a new class of chiral substituted-1,16-dihedroxytetraphenylenes
(S)-2,15-Br2-DHTP 1, (S)-2,15-Cl2-DHTP 6, (S)-2,15-Ph2-DHTP 7, (S)-4,13-Br2-DHTP
10 has been successfully synthesized. The optimial catalyst (S)-2,15-Br2-DHTP 1
provided moderate to high yield and good enantioselectivities for the asymmetric
allylboration of ketones under mild reaction conditions with a broad range of aromatic
ketones. Further work using (S)-2,15-Br2-DHTP 1 as an organocatalyst or a chiral
ligand for other catalytic asymmetric C-C bond-forming reactions is in progress in our
laboratories.
EXPERIMENTAL SECTION
General Information. Chiral HPLC analysis was recorded on a Shimadzu HPLC
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 29
1
2
3
4
5
System using a Chiralpak® IC, Chiralpak® AD-H, Chiralcel® OD-H or Chiralcel®
6
7
1
OJ-H column. Optical rotations were recorded on an Insmark polarimeter. H NMR
8
9
spectra were measured on a 400 MHz or 600 MHz spectrometer. Chemical shifts are
reported in ppm from tetramethylsilane with the solvent resonance as the internal
standard (CDCl3, δ = 7.26). Data are presented as follows: chemical shift (ppm),
multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, brs = broad
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
13
singlet), coupling constants in hertz (Hz), integration, assignment. C NMR spectra
were measured at 100 MHz or 150 MHz. Chemical shift are reported in ppm from
tetramethylsilane with the solvent resonance as the internal standard (CDCl3, δ =
77.16). High-resolution mass spectra (HRMS) were recorded with a Thermo Fisher
Scientific LTQ FT Ultra (ESI) mass spectrometer, Agilent Technologies 6224 TOF
LC/MS spectrometer or Bruker Daltonics FTMS-7 mass spectrometer. Low-resolution
mass spectrometry (LRMS) were measured on an Agilent Single Quad 1260 LC-MS.
Flash chromatography (FC) was performed using silica gel (300-400 mesh). All
reactions were performed under an atmosphere of nitrogen using standard Schlenk
techniques. Commercially available ketones 2a-r were used as received. The starting
material of B-allyl-1,3,2-dioxaborinane 3 was prepared according to literature
procedure.10b (S,S)-1,8,9,16-tetrahydroxytetraphenylene 12 ((S,S)-THTP) and
(S)-1,16-dihydroxy tetraphenylene 5 ((S)-DHTP) were prepared according to the
literature.5c
Synthesis of (S)-2,15-dichlorotetraphenylene-1,16-diol (
6
).6 To a solution of
(S)-DHTP (33.6 mg, 0.1 mmol), catalyst diisopropylamine hydrochloride (1.3
5
mg, 0.01 mmol, 10 mol%) in toluene (2 mL) was added 1,3-dichloro-5,5-
ACS Paragon Plus Environment

Page 13 of 29
The Journal of Organic Chemistry
1
2
3
4
5
o
dimethylhydantoin (DCDMH, 39.4 mg, 0.2 mmol, 2.0 equiv.) at 0 C in the
6
7
o
absence of light. The mixture was stirred at 0 C for 12 h and quenched by
8
9
saturated aqueous Na2SO3 (5 mL). The solution was diluted with water (5 mL)
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
and extrated with EtOAc (3
×10 mL). The combined organic extracts were
washed with brine, dried with anhydrous Na2SO4, filtered and concentrated in
vacuo. The residue was purified by flash chromatography (petroleum
ether/EtOAc = 10:1) to give the compound
6 (28.4 mg, 70% yield) as a colorless
o
solid. mp 212-213 C. HPLC (Chiralpak IC, hexane/i-PrOH = 90:10, flow rate
1.0 mL/min, λ = 254 nm) tR (major) = 6.64 min, tR (minor) = 7.58 min, ee = 99%;
27
[α]D = 39.2 (c 1.0, CH2Cl2). Data is consistent with the known racemic
compound reported in the literature.6 1H NMR (400 MHz, CDCl3) δ 7.32-7.22 (m,
8H), 7.12-7.10 (m, 2H), 6.74 (d, J = 8.0 Hz, 2H), 5.49 (s, 2H); 13C {1H} NMR
(150 MHz, CDCl3) δ 148.2, 142.9, 141.2, 140.3, 129.3, 128.8, 128.2, 127.9,
127.6, 123.5, 122.2, 119.3; HRMS (ESI) calcd. for C24H13Cl2O2 ([M-H]-):
403.0283, found: 403.0298.
Synthesis of (S)-2,15-dibromotetraphenylene-1,16-diol (
1). To a solution of
(S)-DHTP (67.3 mg, 0.2 mmol) and catalyst diisopropylamine (2.0 mg, 0.01
5
mmol, 10 mol%) in CH2Cl2 (100 mL) at 0 °C was added dropwise a solution of
N-bromosuccinimide (NBS, 72.9 mg, 0.41 mmol, 2.05 equiv.) in CH2Cl2 (100
mL) for 12 h in the absence of light. Immediately after the addition, the reaction
mixture was quenched with saturated aqueous Na2SO3 (10 mL). The solution
was diluted with water (15 mL) and the organic layer was separated, and the
aqueous layer was extracted with EtOAc. The combined extracts were washed
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 29
1
2
3
4
5
6
with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo.
The residue was purified by flash chromatography (petroleum ether/CH2Cl2 =
7
8
9
1:1) to afford compound
1 (70.2 mg, 71% yield) as a colorless solid. mp
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
222-224 °C. HPLC (Chiralpak IC, hexane/i-PrOH = 90:10, flow rate 1.0 mL/min,
λ = 254 nm) tR (major) = 5.66 min, tR (minor) = 7.73 min, ee = 99%; [α]D27 = 43.4
(c 1.0, CH2Cl2). 1H NMR (400 MHz, CDCl3) δ 7.40 (d, J = 8.4 Hz, 2H), 7.31-7.29
(m, 4H), 7.25-7.23 (m, 2H), 7.13-7.11 (m, 2H), 6.69 (d, J = 8.4 Hz, 2H), 5.46 (s,
2H); 13C {1H} NMR (100 MHz, CDCl3) δ 149.1, 143.6, 141.1, 140.3, 131.9, 129.3,
128.2, 127.9, 127.6, 123.5, 122.8, 109.5; HRMS (DART) calcd. for C24H14Br2O2
(M+): 491.9355, found: 491.9355.
Synthesis of (S)-2,15-diphenyltetraphenylene-1,16-diol (
7). A mixture of
compound (74.0 mg, 0.15 mmol), phenylboronic acid (109.7 mg, 0.9 mmol),
1
and K2CO3 (125 mg, 0.9 mmol) in DME (5 mL) and H2O (1 mL) were placed in a
25 mL Schlenk tube equipped with a sealed cap. The mixture was degassed
through a freeze-pump-thaw cycle (three times). Then Pd(OAc)2 (6.7 mg, 0.03
mmol) and tricyclohexyl phosphine (PCy3, 10.5 mg, 0.0375 mmol) were added
under an nitrogen atmosphere. The resulting suspension was heated at 100 °C
for 24 h. After evaporation under reduced pressure, the residue was purified by
flash chromatography (petroleum ether/EtOAc = 10:1) to give compound
7
(66.0 mg, 90% yield) as a colorless solid. mp 138-140 °C. HPLC (Chiralpak
AD-H, hexane/i-PrOH = 80:20, flow rate 1.0 mL/min, λ = 254 nm) tR (minor) =
4.93 min, tR (major) = 6.17 min, ee = 99%; [α]D27 = 84.2 (c 1.0, CH2Cl2). 1H NMR
(600 MHz, CDCl3) δ 7.51 (d, J = 7.2 Hz, 4H), 7.40 (t, J = 7.2 Hz, 4H), 7.32-7.17
ACS Paragon Plus Environment

Page 15 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(m, 12H), 6.90 (d, J = 7.2 Hz, 2H), 5.25 (s, 2H); 13C {1H} NMR (100 MHz, CDCl3)
δ 149.2, 143.8, 141.5, 141.1, 137.4, 130.6, 129.4, 129.3, 128.7, 128.3, 127.7,
127.6, 127.5, 127.4, 122.3, 121.8; HRMS (DART) calcd. for C36H23O2 ([M-H]-):
487.1704, found: 487.1696.
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
Synthesis of (S)-1,16-dimethoxytetraphenylene (8). Compound 5 (336.4 mg,
1 mmol) and K2CO3 (829.3 mg, 6 mmol) were dissolved in acetone (20 mL),
and iodomethane (0.4 mL, 6 mmol) was added in one portion. The resulting
mixture was heated under reflux for 24 h. The mixture was allowed to cool to
room temperature and concentrated in vacuo. The residue was purified by flash
chromatography (petroleum ether/EtOAc = 20:1) to give compound
8 (363.0 mg,
27
99% yield) as a colorless solid. mp 235-236 °C. [α]D = 6.2 (c 1.0, CH2Cl2).
Data is consistent with the known racemic compound reported in the
literature.5c 1H NMR (400 MHz, CDCl3) δ 7.25-7.18 (m, 8H), 7.13-7.09 (m, 2H),
6.80 (dd, J = 14.0, 10.8 Hz, 2H), 3.68 (s, 6H); MS (ESI): m/z = 365.2
[C26H20O2+H]+ ; 387.1 [C26H20O2+Na]+.
Synthesis of (S)-1,16-dimethoxy-4,13-dibromotetraphenylene (
9). To a
solution of compound (36.4 mg, 0.1 mmol) in CH3CN (10 mL) was added
5
N-bromosuccinimide (NBS, 71.2 mg, 0.4 mmol, 4.0 equiv.) in one portion and
the mixture was stirred at room temperature for 12 h. The resulting mixture was
quenched by saturated aqueous Na2SO3 (10 mL), and the volatiles were
removed under reduced pressure. The aqueous solution was extracted with
CH2Cl2, and the combined extracts were washed with brine, dried over
anhydrous Na2SO4, filtered and concentrated under vacuum. The residue was
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 29
1
2
3
4
5
purified by flash chromatography (petroleum ether/CH2Cl2 = 3:1) to give
6
7
compound
9
(52.0 mg, 99% yield). mp 270-272 °C. [α]D27 = 19.4 (c 1.0, CH2Cl2).
8
9
1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 8.8 Hz, 2H), 7.30-7.23 (m, 6H),
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
13
7.18-7.16 (m, 2H), 6.67 (t, J = 8.8 Hz, 2H), 3.69 (s, 6H); C {1H} NMR (100
MHz, CDCl3) δ 155.8, 142.0, 140.9, 139.8, 132.4, 129.0, 128.4, 128.0, 127.9,
126.8, 114.1, 111.9, 56.4; HRMS (DART) calcd. for C26H19O2Br2 ([M+H]+):
520.9746, found: 520.9741.
Synthesis of (S)-4,13-dibromotetraphenylene-1,16-diol (10). To a suspension
of compound
9 (52.2 mg, 0.1 mmol) in CH2Cl2 (10 mL) was added a 1.0 M
CH2Cl2 solution of boron tribromide (BBr3, 2 mL, 2 mmol) dropwise at 0 °C. The
reaction mixture was stirred overnight at room temperature and a clear
brownish red solution was obtained. The reaction mixture was quenched with
water (10 mL) at 0 °C, and then the volatiles were evaporated under reduced
pressure. Colorless solid that precipitated was dissolved by addition of ethyl
acetate (20 mL). The organic layer was separated and the residual aqueous
layer was extracted with ethyl acetate. The combined organic phase was
washed with saturated NaHCO3, brine, dried over anhydrous Na2SO4, filtered
and concentrated under reduced pressure. The resulting residue was purified
by flash chromatography (petroleum ether/EtOAc = 2:1) to give compound 10
(49.0 mg, 99% yield). mp 280-282 °C. HPLC (Chiralpak AD-H, hexane/i-PrOH =
80:20, flow rate 1.0 mL/min, λ = 254 nm) tR (major) = 10.72 min, tR (minor) =
22.76 min, ee = 99%; [α]D27 = 32.5 (c 1.0, CH2Cl2). 1H NMR (400 MHz, CDCl3) δ
7.40 (d, J = 8.8 Hz, 2H), 7.29-7.15 (m, 8H), 6.75 (d, J = 8.8 Hz, 2H), 4.92 (s, 2H);
ACS Paragon Plus Environment

Page 17 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
13C {1H} NMR (100 MHz, CDCl3) δ 151.4, 143.4, 140.7, 139.1, 134.2, 128.8,
128.4, 128.3, 127.1, 123.0, 116.7, 114.7; HRMS (DART) calcd. for C24H13O2Br2
([M-H]-): 490.9288, found: 490.9285.
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
General Procedure for the Asymmetric Allylboration of Ketones. A 10 mL
Schlenk tube was charged with a stirring bar and flushed with nitrogen. To the flask
was added (S)-2,15-dibromotetraphenylene-1,16-diol
1 (0.01 mmol), t-BuOH (0.15
mmol), B-allyl-1,3,2-dioxaborinane (0.2 mmol), and toluene (0.5 mL). The mixture
3
was stirred at 25 °C for 10 min and ketone 2a-r (0.1 mmol) was added directly. The
reaction mixture was kept stirring at 25 °C for 48 h-72 h. After the removal of solvents
via rotary evaporation, the residue was purified through flash column chromatography
on silica gel (eluent: petroleum ether/EtOAc = 30:1- 15:1) to give pure product 4a-r.
(S)-(–)-2-(4-bromophenyl)-pent-4-en-2-ol (4a).10b Compound 4a was purified
by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 92% yield (22.2 mg). HPLC (Chiralcel OJ-H, hexane/i-PrOH =
99:1, flow rate 1.0 mL/min, λ = 220 nm) tR (minor) = 16.32 min, tR (major) =
18.17 min, ee = 98%; [α]D27 = –24.4 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.45 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 5.63-5.56 (m, 1H), 5.13 (d, J =
12.8 Hz, 2H), 2.66-2.44 (m, 2H), 2.09 (s, 1H), 1.52 (s, 3H); MS (ESI): m/z =
241.0 [C11H13BrO+H]+.
(S)-(–)-2-phenylpent-4-en-2-ol (4b).10b Compound 4b was purified by silica
gel chromatography (petroleum ether/EtOAc = 20:1) to afford a colorless oil in
94% yield (15.3 mg). HPLC (Chiralpak AD-H, hexane/i-PrOH = 98:2, flow rate
0.8 mL/min, λ = 214 nm) tR (minor) = 11.49 min, tR (major) = 12.11 min, ee =
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 29
1
2
3
4
5
6
7
8
9
99%; [α]D27 = –16.8 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.45-7.42 (m,
2H), 7.36-7.32 (m, 2H), 7.26-7.22 (m, 1H), 5.64-5.58 (m, 1H), 5.16-5.10 (m, 2H),
2.71-2.47 (m, 2H), 1.97 (s, 1H), 1.55 (s, 3H); MS (ESI): m/z = 185.1
[C11H14O+Na]+.
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
(S)-(–)-2-(4-fluorophenyl)-pent-4-en-2-ol (4c).13a Compound 4c was purified
by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 94% yield (17.0 mg). HPLC (Chiralcel OJ-H, hexane/i-PrOH =
98:2, flow rate 0.6 mL/min, λ = 214 nm) tR (minor) = 14,51 min, tR (major) =
15.17 min, ee = 91%; [α]D27 = –4.7 (c 0.5, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.42-7.38 (m, 2H), 7.04-6.99 (m, 2H), 5.63-5.56 (m, 1H), 5.15-5.12 (m, 2H),
2.66-2.46 (m, 2H), 1.54 (s, 3H); MS (ESI): m/z = 203.1 [C11H13FO+Na]+.
(S)-(–)-2-(4-chlorophenyl)-pent-4-en-2-ol (4d).13a Compound 4d was purified
by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 89% yield (17.6 mg). HPLC (Chiralcel OJ-H, hexane/i-PrOH =
99:1, flow rate 0.8 mL/min, λ = 214 nm) tR (minor) = 17.22 min, tR (major) =
18.54 min, ee = 96%; [α]D27 = –26.4 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.38-7.35 (m, 2H), 7.31-7.29 (m, 2H), 5.60-5.56 (m, 1H), 5.15-5.10 (m, 2H),
2.67-2.45 (m, 2H), 2.02 (s, 1H), 1.52 (s, 3H); MS (ESI): m/z = 219.1
[C11H13ClO+Na]+.
(S)-(–)-2-(3-chlorophenyl)-pent-4-en-2-ol (4e).13a Compound 4e was purified
by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 89% yield (17.5 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH =
97:3, flow rate 0.8 mL/min, λ = 214 nm) tR (major) = 8.64 min, tR (minor) = 9.37
ACS Paragon Plus Environment

Page 19 of 29
The Journal of Organic Chemistry
1
2
3
4
5
1
min, ee = 96%; [α]D27 = –24.6 (c 1.0, CHCl3); H NMR (400 MHz, CDCl3) δ
6
7
8
9
7.46-7.45 (m, 1H), 7.31-7.20 (m, 3H), 5.63-5.55 (m, 1H), 5.17-5.12 (m, 2H),
2.68-2.45 (m, 2H), 2.03 (s, 1H), 1.53 (s, 3H); MS (ESI): m/z = 219.1
[C11H13ClO+Na]+.
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
(S)-(–)-2-(2-bromophenyl)-pent-4-en-2-ol (4f).10b Compound 4f was purified
by silica gel chromatography (petroleum ether/EtOAc = 30:1) to afford a
colorless oil in 50% yield (12.0 mg). HPLC (Chiralpak AD-H, hexane/i-PrOH =
98:2, flow rate 0.8 mL/min, λ = 214 nm) tR (minor) = 10.16 min, tR (major) =
11.72 min, ee = 87%; [α]D27 = –7.7 (c 0.5, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.70 (dd, J = 8.0, 1.6 Hz, 1H), 7.58 (dd, J = 8.0, 1.2 Hz, 1H), 7.31-7.25 (m, 1H),
7.09 (td, J = 8.0, 2.0 Hz, 1H), 5.58-5.50 (m, 1H), 5.17-50.7 (m, 2H), 3.28 (dd, J
= 14, 6.4 Hz, 1H), 2.65 (dd, J = 14, 8.4 Hz, 1H), 2.60 (br s, 1H), 1.72 (s, 3H); MS
(ESI): m/z = 263.0 [C11H13BrO+Na]+.
(S)-(–)-2-(4-methylphenyl)-pent-4-en-2-ol (4g).13b Compound 4g was purified
by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 82% yield (14.2 mg). HPLC (Chiralcel OJ-H, hexane/i-PrOH =
99:1, flow rate 0.8 mL/min, λ = 214 nm) tR (minor) = 13.87 min, tR (major) =
18.52 min, ee = 97%; [α]D27 = –31.3 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.32 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 5.63-5.59 (m, 1H), 5.15-5.08
(m, 2H), 2.69-2.45 (m, 2H), 2.33 (s, 3H), 2.01 (s, 1H), 1.52 (s, 3H); MS (ESI):
m/z = 199.1 [C12H16O+Na]+.
(S)-(–)-2-(4-methoxyphenyl)-pent-4-en-2-ol (4h).10b Compound 4h was
purified by silica gel chromatography (petroleum ether/EtOAc = 15:1) to afford a
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 29
1
2
3
4
5
6
7
8
9
colorless oil in 84% yield (16.2 mg). HPLC (Chiralcel OJ-H, hexane/i-PrOH =
98:2, flow rate 0.8 mL/min, λ = 214 nm) tR (minor) = 19.70 min, tR (major) =
25.59 min, ee = 95%; [α]D26 = –16.7 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.38-7.34 (m, 2H), 6.90-6.86 (m, 2H), 5.69-5.58 (m, 1H), 5.15-5.10 (m, 2H),
3.80 (s, 3H), 2.68-2.46 (m, 2H), 2.02 (s, 1H), 1.53 (s, 3H); MS (ESI): m/z =
215.1 [C12H16O2+Na]+.
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
(S)-(–)-2-(naphthalen-2-yl)-pent-4-en-2-ol (4i).10a Compound 4i was purified
by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 90% yield (19.1 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH =
95:5, flow rate 0.8 mL/min, λ = 214 nm) tR (major) = 13.59 min, tR (minor) =
17.66 min, ee = 97%; [α]D27 = –24.4 (c 1.4, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.93-7.83 (m, 4H), 7.55 (dd, J = 8.8, 2.0 Hz, 1H), 7.51-7.45 (m, 2H), 5.69-5.58
(m, 1H), 5.20-5.11 (m, 2H), 2.84-2.57 (m, 2H), 2.10 (brs, 1H), 1.55 (s, 3H); MS
(ESI): m/z = 235.1 [C15H16O+Na]+.
(S)-(–)-2-(naphthalen-1-yl)-pent-4-en-2-ol (4j).8c Compound 4j was purified
by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 38% yield (8.1 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH =
95:5, flow rate 0.8 mL/min, λ = 214 nm) tR (major) = 11.93 min, tR (minor) =
13.79 min, ee = 57%; [α]D27 = –2.4 (c 0.8, CHCl3); 1H NMR (400 MHz, CDCl3) δ
8.75 (d, J = 8.8 Hz, 1H), 7.89-7.87 (m, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.61-7.40
(m, 4H), 5.71-5.63 (m, 1H), 5.18-5.10 (m, 2H), 3.16-2.81 (m, 2H), 2.24 (brs, 1H),
1.84 (s, 3H); MS (ESI): m/z = 235.1 [C15H16O+Na]+.
ACS Paragon Plus Environment

Page 21 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(S)-(–)-2-thiophen-2-yl-pent-4-en-2-ol (4k).10b Compound 4k was purified by
silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a colorless
oil in 71% yield (12.0 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH = 98:2, flow
rate 0.8 mL/min, λ = 214 nm) tR (minor) = 11.97 min, tR (major) = 12.75 min, ee =
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
90%; [α]D26 = –16.3 (c 1.0, CHCl3); H NMR (400 MHz, CDCl3) δ 7.19 (dd, J =
5.2, 1.6 Hz, 1H), 6.96-6.91 (m, 2H), 5.79-5.68 (m, 1H), 5.18-5.13 (m, 2H),
2.73-2.54 (m, 2H), 2.17 (brs, 1H), 1.62 (s, 3H); MS (ESI): m/z = 190.9
[C9H12SO+Na]+.
(S)-(–)-3-(4-methylphenyl)hex-5-en-3-ol (4l). Compound 4l was purified by
silica gel chromatography (petroleum ether/EtOAc = 30:1) to afford a colorless
oil in 79% yield (15.4 mg). HPLC (Chiralcel OJ-H, hexane/i-PrOH = 99:1, flow
rate 0.8 mL/min, λ = 214 nm) tR (minor) = 9.00 min, tR (major) = 9.64 min, ee =
97%; [α]D27 = –13.9 (c 0.5, CHCl3); 1H NMR (600 MHz, CDCl3) δ 7.26 (d, J = 7.8
Hz, 2H), 7.14 (d, J = 7.8 Hz, 2H), 5.62-5.55 (m, 1H), 5.14-5.08 (m, 2H),
2.71-2.45 (m, 2H), 2.33 (s, 3H), 1.92 (s, 1H), 1.86-1.79 (m, 2H), 0.76 (t, J = 7.2
Hz, 3H); 13C {1H} (100 MHz, CDCl3) δ 142.9, 136.0, 133.9, 128.9, 125.5, 119.5,
76.0, 47.0, 35.4, 21.1, 8.0; HRMS (ESI) calcd. for C13H18ONa ([M+Na]+):
213.1250, found: 213.1253.
(S)-(–)-4-penyloct-1-en-4-ol (4m).10b Compound 4m was purified by silica gel
chromatography (petroleum ether/EtOAc = 30:1) to afford a colorless oil in 93%
yield (19.0 mg). HPLC (Chiralpak AD-H, hexane/i-PrOH = 99:1, flow rate 0.8
mL/min, λ = 214 nm) tR (minor) = 10.54 min, tR (major) = 11.31 min, ee = 98%;
1
[α]D27 = –20.4 (c 0.8, CHCl3); H NMR (600 MHz, CDCl3) δ 7.39-7.25 (m, 4H),
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 29
1
2
3
4
5
6
7
8
9
7.16-7.14 (m, 1H), 5.51-5.47 (m, 1H), 5.07-5.02 (m, 2H), 2.73-2.48 (m, 2H),
1.97 (brs, 1H), 1.85-1.75 (m, 2H), 1.26-1.03 (m, 4H), 0.82 (t, J = 7.2 Hz, 3H);
MS (ESI): m/z = 227.1 [C14H20O+Na]+.
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
(S)-(–)-1-allyl-2,3-dihydro-1H-inden-1-ol (4n).10b Compound 4n was purified
by silica gel chromatography (petroleum ether/EtOAc = 15:1) to afford a
colorless oil in 83% yield (14.4 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH =
98:2, flow rate 0.8 mL/min, λ = 214 nm) tR (minor) = 12.07 min, tR (major) =
14.97 min, ee = 91%; [α]D27 = –1.4 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.33-7.31 (m, 1H), 7.25-7.22 (m, 3H), 5.90-5.79 (m, 1H), 5.18-5.13 (m, 2H),
3.02-2.76 (m, 2H), 2.65-2.47 (m, 2H), 2.35-2.04 (m, 2H),1.99 (brs, 1H); MS
(ESI): m/z = 197.1 [C12H14O+Na]+.
(S)-(–)-1-allyl-1,2,3-tetrahydronaphthalen-1-ol (4o).10b Compound 4o was
purified by silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a
colorless oil in 91% yield (17.2 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH =
98:2, flow rate 0.8 mL/min, λ = 214 nm) tR (minor) = 12.19 min, tR (major) =
13.13 min, ee = 96%; [α]D27 = –13.4 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.54 (dd, J = 7.6, 1.6 Hz, 1H), 7.23-7.14 (m, 3H), 5.85-5.77 (m, 1H), 5.17-5.12
(m, 2H), 2.85-2.71 (m, 2H), 2.63-2.60 (m, 2H), 2.08-1.79 (m, 5H); MS (ESI): m/z
= 211.1 [C13H16O+Na]+.
(S)-(–)-1,3-diphenylhexa-5-en-3-ol (4p). Compound 4p was purified by silica
gel chromatography (petroleum ether/EtOAc = 20:1) to afford a colorless oil in
91% yield (23.0 mg). HPLC (Chiralpak AD-H, hexane/i-PrOH = 99:1, flow rate
0.8 mL/min, λ = 214 nm) tR (major) = 22.79 min, tR (minor) = 24.61 min, ee =
ACS Paragon Plus Environment

Page 23 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
98%; [α]D28 = –25.9 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.45-7.35 (m,
4H), 7.27-7.21 (m, 3H), 7.15-7.08 (m, 3H), 5.60-5.51 (m, 1H), 5.18-5.10 (m, 2H),
2.77-2.62 (m, 2H), 2.56-2.29 (m, 2H), 2.15-2.07 (m, 3H); 13C {1H} NMR (100
MHz, CDCl3) δ 145.7, 142.6, 133.4, 128.5, 128.47, 128.46, 126.7, 125.8, 125.4,
120.0, 75.8, 47.8, 44.8, 30.1; HRMS (ESI) calcd. for C18H20ONa ([M+Na]+):
275.1406, found: 275.1405.
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
(S)-(–)-3-methyl-1-phenylhexa-1,5-dien-3-ol (4q).8c Compound 4q was
purified by silica gel chromatography (petroleum ether/EtOAc = 15:1) to afford a
colorless oil in 90% yield (17.0 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH =
95:5, flow rate 0.8 mL/min, λ = 214 nm) tR (minor) = 13.27 min, tR (major) =
15.25 min, ee = 62%; [α]D26 = –20.7 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ
7.39-7.21 (m, 5H), 6.59 (d, J = 16.0 Hz, 1H), 6.29 (d, J = 16.0 Hz, 1H),
5.87-5.78 (m, 1H), 5.18-5.14 (m, 2H), 2.47-2.33 (m, 2H), 1.84 (brs, 1H), 1.38 (s,
3H); MS (ESI): m/z = 227.1 [C13H16O+K]+.
(S)-(–)-1,3-diphenylhexa-1,5-dien-3-ol (4r).13c Compound 4r was purified by
silica gel chromatography (petroleum ether/EtOAc = 20:1) to afford a colorless
oil in 24% yield (6.0 mg). HPLC (Chiralcel OD-H, hexane/i-PrOH = 95:5, flow
rate 0.8 mL/min, λ = 214 nm) tR (major) = 13.33 min, tR (minor) = 15.95 min, ee =
75%; [α]D26 = 1.2 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.52-7.50 (m, 2H),
7.39-7.21 (m, 8H), 6.65 (d, J = 16.0 Hz, 1H), 6.52 (d, J = 16.0 Hz, 1H),
5.75-5.68 (m, 1H), 5.23-5.16 (m, 2H), 2.86-2.74 (m, 2H), 2.28 (brs, 1H); 13C {1H}
NMR (100 MHz, CDCl3) δ 145.4, 136.9, 135.3, 133.2, 128.7, 128.5, 128.4,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 24 of 29
1
2
3
4
5
6
127.7, 127.1, 126.7, 125.6, 120.3, 75.8, 47.3; HRMS (ESI) calcd. for
C18H18ONa ([M+Na]+): 273.1250, found: 273.1243.
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
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications
website at DOI: .
Copies of HPLC, 1H NMR and 13C NMR traces, X-ray crystal structures of compounds
(±)-1 and (±)-10 (PDF).
X-ray crystal details for compound (±)-1 and (±)-10 (CIF).
AUTHOR INFORMATION
Corresponding Author
* E-mail: changjunbiao@zzu.edu.cn
ORCID
Guo-Li Chai: 0000-0002-1342-6217
Junbiao Chang: 0000-0001-6236-1256
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by research fund from Henan Normal University
(5101034011009) and National Postdoctoral Program for Innovative Talents
ACS Paragon Plus Environment

Page 25 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(BX201700071). We thank Professor Henry N.C. Wong (The Chinese
University of Hong Kong and Shanghai-Hong Kong Joint Laboratory in
Chemical Synthesis, Shanghai Institute of Organic Chemistry, The Chinese
Academy of Sciences) for helpful discussion.
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
REFERENCES
(1) For reviews, see: (a) Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Comprehensive
Asymmetric Catalysis; Springer: Berlin, 1999. (b) Ojima, I. Catalytic Asymmetric
Synthesis; Wiley-VCH: Weinheim, 2000. (c) Zhou, Q.-L. Privileged Chiral Ligands and
Catalysts; Wiley-VCH: Weinheim, 2011.
(2) (a) List, B. Introduction: Organocatalysis. Chem. Rev. 2007, 107, 5413-5415.
(b) MacMillan, D. W. C. The Advent and Development of Organocatalysis. Nature
2008, 455, 304-308.
(3) (a) Parmar, D.; Sugiono, E.; Raja, S.; Rueping, M. Complete Field Guide to
Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis:
History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen
Bonding, Ion Pairing, and Metal Phosphates. Chem. Rev. 2014, 114, 9047-9153.
(b) Chen, D.-F.; Han, Z.-Y.; Zhou, X. L.; Gong, L.-Z. Asymmetric Organocatalysis
Combined with Metal Catalysis: Concept, Proof of Concept, and Beyond. Acc.
Chem. Res. 2014, 47, 2365-2377. (c) List, B.; Reisinger, C. M.; Kampen, D. Chiral
Brønsted Acids for Asymmetric Organocatalysis; Springer Link, 2009; Vol. 291. (d)
Brunel, J. M. BINOL: A Versatile Chiral Reagent. Chem. Rev. 2005, 105, 857-897.
(e) Chen, Y.; Yekta, S.; Yudin, A. K. Modified BINOL Ligands in Asymmetric
Catalysis. Chem. Rev. 2003, 103, 3155-3212.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 26 of 29
1
2
3
4
5
6
7
8
9
(4) (a) Han, J.-W.; Chen, J.-X.; Li, X.; Peng, X.-S.; Wong, H. N. C. Recent
Developments and Applications of Chiral Tetraphenylenes. Synlett 2013, 24,
2188-2198. (b) Han, J.-W.; Li, X.; Wong, H. N. C. Our Expedition in
Eight-Membered Ring Compounds: From Planar Dehydrocyclooctenes to
Tub-Shaped Chiral Tetraphenylenes. Chem. Rec. 2015, 15, 107-131. (c) Han,
J.-W.; Peng, X.-S.; Wong, H. N. C. Synthesis of Tetraphenylene Derivatives and
Their Recent Advances. Natl. Sci. Rev. 2017, 4, 892-916.
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
(5) (a) Peng, H.-Y; Lam, C.-K.; Mak, T. C. W.; Cai, Z.; Ma, W.-T; Li, Y.-X; Wong, H. N.
C. Chiral Rodlike Platinum Complexes, Double Helical Chains, and Potential
Asymmetric Hydrogenation Ligand Based on “Linear” Building Blocks:
1,8,9,16-Tetrahydroxytetraphenylene and 1,8,9,16-Tetrakis(diphenylphosphino)
tetraphenylene. J. Am. Chem. Soc. 2005, 127, 9603-9611. (b) Hau, C.-K.; He, H.; Lee,
A. W. M.; Chik, D. T. W.; Cai, Z.; Wong, H. N. C. Enantioselective Brønsted Base
Catalyzed [4+2] Cycloaddition Using Novel Amino-Substituted Tetraphenylene
Derivatives. Tetrahedron 2010, 66, 9860-9874. (c) Chai, G.-L.; Han, J.-W.; Wong, H.
N. C. Hydroxytetraphenylenes as Chiral Ligands: Application to Asymmetric Darzens
Reaction of Diazoacetamide with Aldehydes. Synthesis 2017, 49, 181-187. (d) Chai,
G.-L.; Han, J.-W.; Wong, H. N. C. Asymmetric Darzens Reaction of Isatins with
Diazoacetamides Catalyzed by Chiral BINOL−Titanium Complex. J. Org. Chem. 2017,
82, 12647-12654.
(6) Xiong, X.; Yeung, Y.-Y. Ammonium Salt-Catalyzed Highly Practical Ortho-Selective
Monohalogenation and Phenylselenation of Phenols: Scope and Applications. ACS
Catal. 2018, 8, 4033-4043.
ACS Paragon Plus Environment

Page 27 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(7) (a) Kennedy, J. W.; Hall, D. G. Recent Advances in the Activation of Boron and
Silicon Reagents for Stereocontrolled Allylation Reactions. Angew. Chem., Int. Ed.
2003, 42, 4732-4739. (b) Rauniyar, V.; Hall, D. G. Lewis Acids Catalyze the Addition of
Allylboronates to Aldehydes by Electrophilic Activation of the Dioxaborolane in a
Closed Transition Structure. J. Am. Chem. Soc. 2004, 126, 4518-4519. (c) Rauniyar,
V.; Hall, D. G. Catalytic Enantioselective and Catalyst-Controlled Diastereofacial-
Selective Additions of Allyl- and Crotylboronates to Aldehydes Using Chiral Brønsted
Acids. Angew. Chem., Int. Ed. 2006, 45, 2426-2428. (d) Ishiyama, T.; Ahiko, T.-a.;
Miyaura, N. Acceleration Effect of Lewis Acid in Allylboration of Aldehydes:
Catalytic, Regiospecific, Diastereospecific, and Enantioselective Synthesis of
Homoallyl Alcohols. J. Am. Chem. Soc. 2002, 124, 12414-12415. (e) Jain, P.; Antilla,
J. C. Chiral Brønsted Acid-Catalyzed Allylboration of Aldehydes. J. Am. Chem. Soc.
2010, 132, 11884-11886. (f) Yus, M.; González-Gómez, J. C.; Foubelo, F. Catalytic
Enantioselective Allylation of Carbonyl Compounds and Imines. Chem. Rev. 2011, 111,
7774-7854. (g) Huo, H. X.; Duvall, J. R.; Huang, M. Y.; Hong, R. Catalytic Asymmetric
Allylation of Carbonyl Compounds and Imines with Allylic Boronates. Org. Chem.
Front. 2014, 1, 303-320.
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) (a) Silverio, D. L.; Torker, S.; Pilyugina, T.; Vieira, E. M.; Snapper, M. L.; Haeffner,
F.; Hoveyda, A. H. Simple Organic Molecules as Catalysts for Enantioselective
Synthesis of Amines and Alcohols. Nature 2013, 494, 216-221. (b) van der Mei, F. W.;
Miyamoto, H.; Silverio, D. L.; Hoveyda, A. H. Lewis Acid Catalyzed Borotropic Shifts in
the Design of Diastereo- and Enantioselective γ-Additions of Allylboron Moieties to
Aldimines. Angew. Chem., Int. Ed. 2016, 55, 4701-4706. (c) Robbins, D. W.; Lee, K.;
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 28 of 29
1
2
3
4
5
6
7
8
9
Silverio, D. L.; Volkov, A.; Torker, S.; Hoveyda, A. H. Practical and Broadly Applicable
Catalytic Enantioselective Additions of Allyl-B(pin) Compounds to Ketones and
α-Ketoesters. Angew. Chem., Int. Ed. 2016, 55, 9610-9614. (d) Lee, K.; Silverio, D. L.;
Torker, S.; Robbins, D. W.; Haeffner, F.; van der Mei, F. W.; Hoveyda, A. H. Catalytic
Enantioselective Addition of Organoboron Reagents to Fluoroketones Controlled by
Electrostatic Interactions. Nat. Chem. 2016, 8, 768-777. (e) van der Mei, F. W.; Qin,
C.; Morrison, R. J.; Hoveyda, A. H. Practical, Broadly Applicable, α‑Selective, Z‑
Selective, Diastereoselective, and Enantioselective Addition of Allylboron Compounds
to Mono‑, Di‑, Tri‑, and Polyfluoroalkyl Ketones. J. Am. Chem. Soc. 2017, 139,
9053-9065.
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
(9) Wu, T. R.; Shen, L.; Chong, J. M. Asymmetric Allylboration of Aldehydes and
Ketones Using 3,3'-Disubstitutedbinaphthol-Modified Boronates. Org. Lett. 2004, 6,
2701-2704.
(10) (a) Lou, S.; Moquist, P. N.; Schaus, S. E. Asymmetric Allylboration of Ketones
Catalyzed by Chiral Diols. J. Am. Chem. Soc. 2006, 128, 12660-12661. (b) Barnett, D.
S.; Moquist, P. N.; Schaus, S. E. The Mechanism and an Improved Asymmetric
Allylboration of Ketones Catalyzed by Chiral Biphenols. Angew. Chem., Int. Ed. 2009,
48, 8679-8682. (c) Paton, R. S.; Goodman, J. M.; Pellegrinet, S. C. Mechanistic
Insights into the Catalytic Asymmetric Allylboration of Ketones: Brønsted or Lewis
Acid Activation? Org. Lett. 2009, 11, 37-40.
(11) Zhang, Y.; Li, N.; Qu, B.; Ma, S.; Lee, H.; Gonnella, N. C.; Gao, J.; Li, W.; Tan, Z.;
Reeves, J. T.; Wang, J.; Lorenz, J. C.; Li, G.; Reeves, D. C.; Premasiri, A.; Grinberg,
N.; Haddad, N.; Lu, B. Z.; Song, J. J.; Senanayake, C. H. Asymmetric Methallylation
ACS Paragon Plus Environment

Page 29 of 29
The Journal of Organic Chemistry
1
2
3
4
5
6
7
of Ketones Catalyzed by a Highly Active Organocatalyst 3,3'‑F2‑BINOL. Org. Lett.
2013, 15, 1710-1713.
8
9
(12) (a) lam, . ollgra , . riksson, L. ab , K. J. Synthesis of Adjacent
Quaternary Stereocenters by Catalytic Asymmetric Allylboration. J. Am. Chem. Soc.
2015, 137, 11262-11265. (b) Diner, C., Szabó, K. J. Recent Advances in the
Preparation and Application of Allylboron Species in Organic Synthesis. J. Am.
Chem. Soc. 2017,139, 2-14. (c) Huang, G.; Diner, C.; Szabó, K. J. Mechanism and
Stereoselectivity of the BINOL-Catalyzed Allylboration of Skatoles. Org. Lett. 2017, 19,
5904-5907.
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
(13) (a) Zhang X, Chen D, Liu X, Feng X. Enantioselective Allylation of Ketones
Catalyzed by N,N'-Dioxideand Indium(III) Complex. J. Org. Chem. 2007, 72, 5227
-5233. (b) Shi, S.-L., Xu, L.-W., Oisaki, K., Kanai, M., Shibasaki, M. Identification of
Modular Chiral Bisphosphines Effective for Cu(I)-Catalyzed Asymmetric Allylation and
Propargylation of Ketones. J. Am. Chem. Soc. 2010,132, 6638-6639. (c) Sasaki, M.,
Higashi, M., Masu, H., Yamaguchi, K., Takeda, K. Asymmetric [2,3]-Wittig
Rearrangement Induced by a Chiral Carbanion Whose Chirality Was Transferred from
an Epoxide. Org. Lett. 2005, 7, 5913-5915.
ACS Paragon Plus Environment