Catalytic enantioselective bromohydroxylation of cinnamyl alcohols

Article abstract of DOI:10.1039/d1ra02297k

This work describes an effective enantioselective bromohydroxylation of cinnamyl alcohols with (DHQD)₂PHAL as the catalyst and H₂O as the nucleophile, providing a variety of corresponding optically active bromohydrins with up to 95% ee.

Full text of DOI:10.1039/d1ra02297k

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Catalytic enantioselective bromohydroxylation of
cinnamyl alcohols†
Cite this: RSC Adv., 2021, 11, 13040
a
ab
*
and Yian Shi
Jing Li
Received 23rd March 2021
Accepted 23rd March 2021
This work describes an effective enantioselective bromohydroxylation of cinnamyl alcohols with
(DHQD)2PHAL as the catalyst and H2O as the nucleophile, providing a variety of corresponding optically
active bromohydrins with up to 95% ee.
DOI: 10.1039/d1ra02297k
rsc.li/rsc-advances
Electrophilic halogenation of olens allows installation of two only a few reports.6,7 As part of our general intertest in asym-
stereogenic centers onto the C–C double bond and is one of the metric halogenation,8 recently we have been investigating the
most important transformations in organic chemistry.1 Opti- intermolecular asymmetric reaction processes, particularly with
cally active halogen containing products resulting from asym- unfunctionalized olens, which has been a long standing
metric halogenation would serve as versatile chiral building challenging problem. During such studies, we have found that
blocks for organic synthesis. As a result, extensive efforts have up to 92% ee could be achieved for the bromoesterication of
been devoted to the development of asymmetric halogenation unfunctionalized olens with (DHQD)2PHAL (Scheme 2, eqn
process. In recent years, great progress has been made in both (a)).9 This work represents an early example of asymmetric
intramolecular2,3 and intermolecular4,5 reaction processes with halogenation for unfunctionalized olens with high enantio-
various types of olens and nucleophiles. However, there are selectivity. To our delight, high enantioselectivity can also be
still challenges remaining to be addressed. In many cases, the achieved for bromohydroxylation with H2O upon further
developed catalytic systems oen only apply to certain ranges of investigation, giving optically active bromohydrins with up to
substrates and the reaction reactivity as well as selectivity can't 98% ee (Scheme 2, eqn (b)).10 In our efforts to expand the
be rationally adjusted. The substrate scope is also oen difficult reaction scope of the asymmetric bromohydroxylation, we have
to be logically extended and requires much experimentation, found that cinnamyl alcohols are effective substrates, giving the
largely due to the complexity of the reaction systems and the corresponding bromohydrins with up to 95% ee. Herein, we
lack of clear understanding of the reaction mechanisms.
report our preliminary studies on this subject.
Halohydroxylation of olens simply with H2O as nucleophile
Initial studies were carried out with (E)-3-(4-bromophenyl)
is a classic electrophilic addition reaction in organic chemistry prop-2-en-1-ol (1a) as substrate. Several bromine reagents were
and produces synthetically useful halohydrins (Scheme 1). examined with 10 mol% (DHQD)2PHAL (3a) (Fig. 1) as the
Asymmetric version of such process has been challenging with catalyst and 10 mol% (ꢀ)-camphorsulfonic acid (CSA) as addi-
ꢁ
tive in acetone/H2O (10 : 1) at ꢀ30 C (Table 1, entries 1–5). N-
Bromobenzamide gave the highest ee (76%) (Table 1, entry 5).
Among the catalysts investigated (Table 1, entries 5–9),
(DHQD)2PHAL (3a) was the choice of the catalyst with N-bro-
mobenzamide. Solvent studies (Table 1, entries 5 and 10–15)
showed that the highest ee (83%) was obtained with
Scheme 1 Asymmetric halohydroxylation of olefins.
aInstitute of Natural and Synthetic Organic Chemistry, Changzhou University,
Changzhou 213164, P. R. China. E-mail: shiyian@cczu.edu.cn
bDepartment of Chemistry, Colorado State University, Fort Collins, Colorado 80523,
USA
† Electronic supplementary information (ESI) available: Experimental,
characteriza-tion data, X-ray structures of 2a, 2e, and 12, HPLC data for
determination of enantiomeric excesses, and NMR spectra. CCDC 1941798,
1963482, and 2027431. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/d1ra02297k
Scheme 2 Asymmetric oxybromination of olefins.
13040 | RSC Adv., 2021, 11, 13040–13046
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(DHQD)2PHAL (3a), N-bromobenzamide (1.2 eq.), and 10 mol%
(ꢀ)-CSA in CH3CN/H2O (10 : 1) at ꢀ30 ꢁC. As shown in Table 2,
the bromohydroxylation can be extended to various cinnamyl
alcohols, giving the corresponding bromohydrins in 46–87%
yields and 55–95% ee's (Table 2, entries 1–17). The reaction
outcome was signicantly inuenced by the substituent on the
phenyl group. In general, the enantioselectivity increased as
a substituent was introduced onto the phenyl group. For mono-
substituted substrates, it appeared that higher ee was obtained
with the para-substituent (Table 2, entry 5 vs. 6 vs. 7). Up to 90%
ee was achieved with p-Ph substituted cinnamyl alcohol (Table
2, entry 4). For 4-substituted substrates, the enantioselectivity
remained similar when a second Me group was introduced to
the 3 position (Table 2, entries 9–12). However, signicantly
higher ee's were obtained when the Me group was introduced to
the 2-position, giving the corresponding bromohydrins in 90–
95% ee (Table 2, entries 13–17). With 2-Me, 4-Br-substituted
cinnamyl alcohol (1m), MeOH was also found to be effective
nucleophile, giving the corresponding bromoether (2r) in 75%
yield and 90% ee (Table 2, entry 18). A similar ee but lower yield
was obtained when the hydroxyl group was replaced with the
MeO group, giving the bromohydrin (2s) in 31% yield and 80%
ee (Table 2, entry 19). The exact reason for this difference is not
clear at this moment.
Fig. 1 Selected examples of catalyst examined.
CH3CN/H2O (10 : 1) (Table 1, entry 10). Addition of 10 mol%
(ꢀ)-CSA increased both yield and ee (Table 1, entry 10 vs. 16).
The best result was obtained with (ꢀ)-CSA among the additives
examined (Table 1, entry 10 vs. entries 17–21). Slightly higher ee
(85%) but lower yield was obtained when the reaction temper-
ꢁ
ature was lowered to ꢀ40 C (Table 1, entry 22 vs. 10).
With the optimized reaction conditions in hand, the
substrate scope was subsequently investigated with 10 mol%
Table 1 Studies on reaction conditionsa
Entry
Cat.
Br source
Additive
Solvent
Yieldb (ee)c %
1
2
3
4
5
6
7
8
3a
3a
3a
3a
3a
3b
3c
3d
NBS
DBDMH
TBCO
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
(ꢀ)-CSA
—
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
Acetone/H2O (10 : 1)
CH3CN/H2O (10 : 1)
EtOAc/H2O (10 : 1)
TFE/H2O (10 : 1)
79 (65)
76 (62)
55 (7)
48 (67)
59 (76)
18 (6)
MeCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
PhCONHBr
9 (0)
35 (ꢀ57)
9
3e (quinidine)
31 (0)
10
11
12
13
14d
15e
16
17
18
19
20
21
22f
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
70 (83)
16 (67)
43 (51)
13 (70)
66 (82)
68 (81)
36 (77)
63 (82)
34 (77)
32 (77)
68 (80)
39 (57)
49 (85)
DCM/H2O (10 : 1)
CH3CN/H2O (5 : 1)
CH3CN/H2O (20 : 1)
CH3CN/H2O (10 : 1)
CH3CN/H2O (10 : 1)
CH3CN/H2O (10 : 1)
CH3CN/H2O (10 : 1)
CH3CN/H2O (10 : 1)
CH3CN/H2O (10 : 1)
CH3CN/H2O (10 : 1)
(+)-CSA
PhCO2H
1-NapCO2H
p-TsOH
AlCl3
(ꢀ)-CSA
a
Reactions were carried out with substrate 1a (0.30 mmol), catalyst (0.030 mmol), additive (0.030 mmol), and Br source (0.36 mmol) in solvent/H2O
(10 : 1) (3.0 mL + 0.3 mL) at ꢀ30 ꢁC for 72 h unless otherwise noted. Isolated yield. c Determined by chiral HPLC analysis. d CH3CN/H2O (5 : 1)
b
(3.0 mL + 0.6 mL). e CH3CN/H2O (20 : 1) (3.0 mL + 0.15 mL). f At ꢀ40 ꢁC for 168 h.
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Table 2 Asymmetric bromohydroxylation of cinnamyl alcoholsa
Entry
Substrate
Product
Yieldb (%)
eec (%)
1
2
3
4d
5
6
7
8
X ¼ p-Br, 1a
X ¼ p-Cl, 1b
X ¼ p-F, 1c
X ¼ p-Ph, 1d
X ¼ p-Me,1e
X ¼ m-Me,1f
X ¼ o-Me,1g
X ¼ H,1h
2a (X-ray)
2b
2c
2d
2e (X-ray)
2f
2g
2h
70
64
75
87
76
71
77
46
83
80
76
90
82
62
70
55
9
X ¼ Br, 1i
X ¼ Cl, 1j
X ¼ F, 1k
X ¼ Me, 1l
2i
2j
2k
2l
70
71
84
73
80
80
80
82
10
11
12
13
14
15
16
17
X ¼ Br, 1m
X ¼ Cl, 1n
X ¼ F, 1o
2m
2n
2o
2p
2q
72
78
83
84
87
95
94
91
94
90
X ¼ Ph, 1p
X ¼ Me, 1q
18e
75
90
19
31
80
a
Reactions were carried out with substrate 1 (0.50 mmol), (DHQD)2PHAL (0.050 mmol), (ꢀ)-CSA (0.050 mmol), and PhCONHBr (0.60 mmol) in
b
c
CH3CN (5.0 mL) and water (0.50 mL) at ꢀ30 ꢁC for 72 h unless otherwise noted. Isolated yield. Determined by chiral HPLC analysis. For
entry 1, the absolute conguration was determined by comparing the optical rotation of the corresponding epoxide with the reported one11
d
upon treatment with K2CO3 in acetone (Scheme 3). For others, the absolute congurations were tentatively assigned by analogy. The reaction
e
was carried out at ꢀ40 ꢁC for 168 h. MeOH was used as nucleophile.
The absolute conguration of bromohydrin 2a was deter-
mined by converting it to the corresponding epoxide 4 with
K2CO3 (Scheme 3) and comparing the optical rotation of the
epoxide with the reported one.11 The bromohydroxylation
reaction can also be carried out on a relatively large scale. For
example, 1.1341 g of bromohydrin 2m was obtained in 70%
yield with 95% ee (Scheme 4). As shown in Scheme 5, bromo-
hydrin 2m can be converted to bromoacetal 5 in 86% yield
Scheme 3 Determination of absolute configuration of bromohydrin
2a.
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Scheme 7 Synthetic transformations of epoxide 9.
Scheme 4 Bromohydroxylation on gram scale.
Scheme 5 Synthetic transformations of bromohydrin 2m.
without loss of the ee. Sulde 6 was obtained in 65% yield and
95% ee when 2m was reacted with sodium thiophenolate.
Optically active bromoether like 2r could also serve as useful
intermediates for further transformations (Scheme 6). Treating
2r with NaN3 in DMF at 80 ꢁC gave azide 7 in 50% yield and 90%
ee with inversion of conguration. The bromide of 2r could also
be converted to chloride 8 in 90% ee while the yield was
somewhat low. Epoxide 9 was obtained in 87% yield and 90% ee
by treatment of 2r with NaOH in dioxane and water. When 2r
was reacted with PhSNa in DMF at 80 ꢁC, sulde 10 was isolated
in 73% yield and 90% ee. The reaction likely proceeded via
epoxide 9. The synthetic application is further illustrated in
Scheme 7. Azide 11 and chloride 12 were obtained from 9 in
80% and 78% yield, respectively, without erosion of the optical
activity.12
A precise understanding of the reaction mechanism awaits
further study. As previously described,10 two possible transition
state models are outlined in Fig. 2. The substrate is likely
docked in the chiral pocket through p,p-stacking with quino-
line of the catalyst. Such p,p-interaction appeared to be
enhanced by the substituents on the phenyl groups, conse-
quently leading to the signicant increase of the enantiose-
lectivity. In model A, N-bromobenzamide was activated by both
the tertiary amine of the catalyst and additive (ꢀ)-CSA to
increase its electrophility toward the double bond of the react-
ing substrate. In model B, the tertiary amine of the catalyst
could rst be protonated by additive (ꢀ)-CSA, and N-
Fig. 2 Two possible transition state models.
bromobenzamide would subsequently be activated by the
resulting quaternary ammonium salt via hydrogen bonding.
Conclusions
In summary, bromohydroxylation of olens is a classic and
important electrophilic addition reaction in organic chemistry.
Asymmetric version of this reaction process has been chal-
lenging. In this work, we have found that cinnamyl alcohols are
effective substrates for asymmetric bromohydroxylation with
(DHQD)2PHAL as catalyst, (ꢀ)-CSA additive, PhCONHBr as
bromine source, and H2O as nucleophile, providing the corre-
sponding optically active bromohydrins with up to 95% ee. The
resulting bromohydrin and related bromoether can be trans-
formed into various highly functionalized molecules with
maintained ee's. The current reaction process represents
a signicant progress in asymmetric bromohydroxylation.
Further understanding reaction mechanism, developing more
effective catalyst system, and expanding the substrate scope are
currently underway.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
We gratefully acknowledge the National Natural Science Foun-
dation of China (21632005) and Changzhou University for the
nancial support. We also thank Miao Zhao at Changzhou
University for some experimental contributions.
Notes and references
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development
of
regio-
and
stereoselective
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13046 | RSC Adv., 2021, 11, 13040–13046
© 2021 The Author(s). Published by the Royal Society of Chemistry