Catalytic asymmetric aldehyde prenylation and application in the total synthesis of (-)-rosiridol and (-)-bifurcadiol

Article abstract of DOI:10.1039/d0cc00367k

Chiral phosphoric acid-catalyzed asymmetric aldehyde prenylation has been established using an α,α-dimethyl allyl boronic ester. The transformation provides expedient access to a wide array of aryl, heteroaryl, aryl-substituted alkenyl and primary and sec

Full text of DOI:10.1039/d0cc00367k

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S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
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DOI: 10.1039/D0CC00367K
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Catalytic Asymmetric Aldehyde Prenylation and Application in
the Total Synthesis of (‒)-Rosiridol and (‒)-Bifurcadiol
Yu-Long Zhang,a Zhen-Ni Zhao,a Wang-Lai Li,a Jing-Jie Li,a Subarna Jyoti Kalita,a Uwe
Received 00th January 20xx,
Accepted 00th January 20xx
Schneiderb and Yi-Yong Huanga,*
DOI: 10.1039/x0xx00000x
tumor activities while its enantiomer (alkannin) has been used as anti-
oxidant, anti-tumor, and anti-thrombotic agents, and in wound
healing.4 (–)-Rosiridol (III) and its glycosylated derivatives inhibit
Chiral phosphoric acid-catalyzed asymmetric aldehyde
prenylation has been established using an α,α-dimethyl allyl
boronic ester. The transformation provides an expedient access
to a wide array of aryl, heteroaryl, aryl-substituted alkenyl as well
as primary and secondary aliphatic homoprenyl alcohols with
excellent asymmetric induction. The utility of this asymmetric
catalysis strategy has been demonstrated through a short and
efficient total synthesis of the two natural products (‒)-rosiridol
and (‒)-bifurcadiol.
monoamine oxidase
B (MAO B), which is involved in
neurodegenerative diseases.5 (–)-Bifurcadiol (IV) displays anti-ulcer
and anti-tumor activities.6 Furaquinocin D (V) shows a wide range of
biological effects including anti-hypertensive activity, inhibition of
platelet aggregation and coagulation.7 Sargachromanol C (VI) has
been identified as a potential anti-cancer and anti-mutagenic agent as
well as an inhibitor of Na+/K+ ATPase and isocitrate lyase.8
In this context, the invention of efficient asymmetric catalysis
methods to assemble enantiomerically enriched homoprenyl alcohols9
and the corresponding natural products or potential drugs represents a
significant task for synthetic organic chemists.10 To date, two types
of synthetic strategies have been documented to achieve this goal;
reduction (C–H bond formation) and C–C bond formation (Scheme
1). The first approach relies on the asymmetric reduction of prenyl
ketones using a stoichiometric amount of a chirally modified B-
based11a–c or Al-based11d reductant; accordingly, the asymmetric total
syntheses of shikonin (II),11a,b alkannin (ent-II),11a,b (–)-rosiridol
(III),11c and (–)-bifurcadiol (IV)11d have been described (Scheme 1–
1). The second approach relies on the use of a chiral reagent or
catalyst in order to access enantioenriched homoprenyl alcohols via
C–C bond formation. Suzuki et al. reported the total synthesis of (–)-
furaquinocin D (V) from an enantioenriched terminal epoxide and an
alkenyl stannane in the presence of stoichiometric amounts of BuLi
and BF3•OEt2 (single example; Scheme 1–2).12 Here, the reaction
proceeds via Sn–Li transmetalation followed by boron-mediated
epoxide ring-opening with the in situ-generated alkenyl lithium
species. Loh et al. reported a HOTf-catalyzed prenylation using
aldehydes and an enantioenriched prenyl 1,5-diol (8 examples;
Scheme 1–3a);13 after initial condensation, the chirality transfer
proceeds via an oxonia-Cope rearrangement followed by hydrolysis
to give the corresponding homoprenyl alcohols (87–98% ee). Cozzi
and Umani-Ronchi et al. reported a catalytic asymmetric Nozaki–
Hiyama reaction using benzaldehyde and prenyl chloride in the
presence of an enantioenriched chromium complex and stoichiometric
amounts of Mn(0) and Me3SiCl to afford the corresponding
homoprenyl alcohol with 42% ee (single example; Scheme 1–3b);14
While catalytic asymmetric prenylation across C=C double bonds
with high asymmetric induction has been established,15 the use of
Enantiomerically enriched homoprenyl alcohols are not only versatile
building blocks,1 but also widely present as key motifs in
pharmaceutically active compounds and natural products (Figure 1).2
OH
O
HO
H
OH
O
OH
O
OH
II
I
inotodiol (
shikonin (
alkannin (ent-
)
)
II
)
OH
OH
HO
HO
2
III
IV
)
(–)-rosiridol (
)
(–)-bifurcadiol (
OH
O
O
O
OH
O
O
OH
2
HO
V
VI
)
furaquinocin D (
)
sargachromanol C (
Figure 1. Selected natural products containing an enantioenriched
homoprenyl alcohol motif.
Indeed, inotodiol (I) displays significant anti-tumor activity, including
human cervical cancer.3 Shikonin (II) exhibits anti-bacterial and anti-
a. Department of Chemistry, School of Chemistry, Chemical Engineering and Life
Science, Wuhan University of Technology, Wuhan 430070, China. E-mail:
huangyy@whut.edu.cn
b. EaStCHEM School of Chemistry, The University of Edinburgh, The King’s Buildings,
David Brewster Road, Edinburgh EH9 3FJ, UK.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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Journal Name
(1) Asymmetric reduction of prenyl ketones (C–H bond formation; refs 11a–d)
OH
OH
View Article Online
4
(R)- (10 mol%)
DOI: 10.1039/D0CC00367K
Ph
O
O
B
O
+
(B or Al) reductant*
Ph
H
4Å MS, solvent
T, time
O
R
R
1a
2
3a
(2) Ring-opening alkenylation of an chiral terminal epoxide (C–C bond formation; ref 12)
Ar
-C
OH
i
BuLi, BF3•OEt2
4a:
4b:
4c:
4d:
Ar = 2,4,6-( Pr)3 6H2
Ar = SiPh3
(R)-
(R)-
(R)-
(R)-
O
Bu
3Sn
+
O
O
O
*R
*R
(3) Asymmetric aldehyde prenylation (C–C bond formation)
(a) Use of an enantioenriched prenyl 1,5-diol and a Brønsted acid catalyst (ref 13)
P
-4-OMe-C
single example
t
OH
Ar = 3,5-( Bu)
6H2
2-C
t
Ar = 3,5-( Bu)2 6H3
Ar
entry
(R)-4
solvent
T
time
/ h
5
yield
/ %[b]
82
ee[c]
/ oC
rt
OH
OH
OH
HOTf (cat.)
O
+
1
2
toluene
toluene
toluene
toluene
toluene
THF
0
-
R
R
H
8 examples
0
12
18
10
13
12
10
20
24
28
30
32
36
38
26
86
92
85
92
89
93
90
94
92
89
93
89
90
92
73
26
56
64
60
48
95
95
96
97
98
76
83
98
4a
4a
4a
4a
4a
4a
4a
4b
4c
4d
4a
4a
4a
4a
alkyl
R = Ar, 1o
87–98% ee
3
0
(b) Use of prenyl chloride in the presence of a chiral Lewis acid catalyst (ref 14)
4
0
5
0
Cr(salen*) (cat.)
OH
O
SiCl
Cl
Mn(0), Me3
6
0
+
Ph
Ph
H
7
CH2Cl2
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
0
single example
8
−20
−30
−40
−50
−60
−60
−60
−60
42% ee
9
(c) This work: use of a prenyl boronic ester and a chiral Brønsted acid catalyst
10
11
12
13[d]
14[e]
15[f]
phosphoric acid*
OH
O
O
O
(cat.)
building blocks
(–)-rosiridol
(–)-bifurcadiol
α
+
B
R
γ
R
H
28 examples
γ
& 2o alkyl: high yields & asymmetric induction
R = Ar, HetAr, Ar–alkenyl, 1o
Scheme 1. Access to enantioenriched homoprenyl alcohols: literature
[a]
background and this work’s approach.
Reaction conditions (unless otherwise specified): 1a (0.10 mmol), 2 (0.15
mmol), (R)-4 (10 mol%), 4Å MS (25 mg), solvent (0.3 mL). [b] Isolated yield.
[c] The enantiomeric excess (ee) was determined by chiral HPLC analysis.
[d]
carbonyl electrophiles to access enantioenriched homoprenyl alcohols
has remained elusive.16 Since the asymmetric γ-regioselective allyl
boration of aldehydes catalyzed by an enantioenriched Brønsted acid
provides a short and efficient access to homoallyl alcohols,17 we have
anticipated the possibility of using an α,α-dimethyl allyl boronic
ester18 to create an unprecedented catalytic entry to homoprenyl
alcohols with high asymmetric induction (Scheme 1–3c).
Accordingly, complex chiral molecules containing a homoprenyl
alcohol motif could be concisely installed by asymmetric catalysis. In
this communication, we describe a simple, general, and highly regio-
and enantioselective aldehyde prenylation controlled by an (R)-
BINOL-derived phosphoric acid catalyst, and applications to the total
synthesis of (–)-rosiridol (III) and (–)-bifurcadiol (IV).
In the absence of 4 Å MS. [e] 5 mol% of (R)-4a. [f] 15 mol% of of (R)-4a.
traces of water display a detrimental effect on the asymmetric
induction, likely by disturbing the H-bond donor ability of the chiral
catalyst. Finally, the effect of the catalyst loading was probed thereby
confirming that 10 mol% was the appropriate amount for this
transformation (entries 14 and 15). The standard reaction conditions
for the following studies refer to the optimized conditions displayed
in entry 12 of Table 1: 1 (1.0 equiv), 2 (1.5 equiv), (R)-4a (10 mol%),
4Å MS, toluene, –60 oC.
The optimal reaction conditions were applied to a wide variety of
aldehydes to probe the versatility of our methods (Scheme 2).
Initially, the effect of diverse substituents at the para, meta, and ortho
positions of the aromatic ring was examined. The use of aromatic
aldehydes bearing para-located electron-donating, neutral, and
electron-withdrawing groups gave the corresponding homoprenyl
alcohols 3b–k with 94–98% ee. Meta-located substituents (MeO, Br,
CN) were also tolerated; the corresponding products 3l–n were
formed with 95–97% ee. The use of aromatic aldehydes with an
ortho-located Me atom and F group gave homoprenyl alcohols 3o and
3p with 96% ee and 90% ee, respectively. The use of 6-
bromopiperonal (1q) under slightly modified conditions provided
product 3q with 90% ee; the absolute configuration of (+)-3q was
determined to be R based on an X-ray crystallographic analysis.19 By
analogy, the absolute configuration of all other aromatic homoprenyl
alcohols was also assigned to be R. Product 3r, derived from 3,4-
dimethylbenzaldehyde, was produced with 99% ee. Naphthalene- and
thiophene-derived aldehydes were converted into the corresponding
homoprenyl alcohols 3s–v with 96–99% ee. In addition, aryl-
substituted alkenyl aldehydes 1w and 1x were used to give the
corresponding products 3w and 3x with 93% ee and 98% ee,
respectively. Finally, challenging primary and secondary aliphatic
In our initial prenylation model study, benzaldehyde (1a) was used
with α,α-dimethyl allyl boronic ester 2 in toluene in the presence of
4Å molecular sieves (Table 1). In the absence of a catalyst,
homoprenyl alcohol 3a (racemic) was formed at room temperature in
82% yield (5 h; entry 1). In order to develop an asymmetric version,
o
a chiral Brønsted acid catalysis strategy was applied at 0 C. In the
presence of 10 mol% of (R)-BINOL-derived chiral phosphoric acid
(R)-4a, product 3a was obtained in 86% yield with 73% ee (entry 2).
The catalytic use of other chiral phosphoric acids (R)-4b–d has proved
less effective (26–64% ee; entries 3–5). Similarly, the reactions using
(R)-4a in THF and DCM gave product 3a in only 60% ee and 48% ee,
respectively (entries 6 and 7). Next, we investigated the effect of the
reaction temperature on the asymmetric induction (entries 8–12).
Gratifyingly, 3a was formed with 95% ee at –20 oC (entry 8); the best
result was obtained at –60 oC over 32 h (93% yield, 98% ee; entry 12).
A control experiment in the absence of 4Å molecular sieves resulted
in the formation of 3a with only 76% ee (entry 13); this result suggests
that
Table 1. Optimization of reaction conditions. [a]
2 | J. Name., 2012, 00, 1-3
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SeO
tBuO2H
,
trityl chloride (TrCl)
Et
aldehydes 1y–z and 1aa were used to provide homoprenyl alcohols
3y–z and 3aa with 84–89% ee.
2
View Article Online
3N, DMAP
salicylic acid
TrO
HO
TrO
DOI: 10.1039/D0CC00367K
OH
DCM, rt, 24 h
96%
DCM, rt, 46 h
40%
5
6
7
Scheme 2. Scope of aldehydes.[a]
Ar
O
(10 mol%)
OH
B
4a
O
B
O
(R)-
O
O
OH
O
O
+
O
MnO2
P
2
R
O
TrO
TrO
R
H
OH
4Å MS, toluene
H
–60 o
C
−
−
z
z
DCM, rt, 36 h
85%
1a
1aa
3a
conditions as in
Table 1, entry 12 (32 h)
4a
2
(R)-
Ar
3aa
Ar = 2,4,6-(
iPr)3 6H2
8
9
-C
89%, 99% ee
OH
OH
OH
OH
OH
HOTf
HO
iPr
MeOH, rt, 26 h
85%
MeO
Me
,
,
32 h
3a
3b
3c
3d
32 h
, 32 h
, 32 h
(–)-rosiridol
III
93% yield, 98% ee
92% yield, 96% ee
95% yield, 98% ee
92% yield, 98% ee
(
)
OH
OH
OH
OH
Scheme 3. Synthetic route to (–)-rosiridol (III).
tBu
SeO
Br
F
Cl
TrCl
3N, DMAP
2, salicylic acid
3e
, 32 h
3f
3g
, 32 h
90% yield, 95% ee
, 32 h
3h
, 32 h
tBuO2H
Et
HO
TrO
TrO
TrO
94% yield, 98% ee
92% yield, 97% ee
91% yield, 94% ee
2
DCM, rt, 32 h
85%
2
DCM, rt, 48 h
45%
OH
OH
OH
OH
10
MeO
11
O
Ph
Br
O2N
F3C
,
,
28 h
OH
B
3i
3j
3l
32 h
, 32 h
93% yield, 95% ee
3k
, 30 h
96% yield, 98% ee
O
O
98% yield, 98% ee
93% yield, 95% ee
MnO2
2
TrO
H
Me
F
OH
OH
OH
OH
2
DCM
rt, 38 h
conditions as in
Table 1, entry 12
2
NC
12
13
(34 h)
92%
3m
3n
3o
3p
, 32 h
95% yield, 90% ee
, 32 h
, 28 h
92% yield, 95% ee
, 32 h
OH
94% yield, 97% ee
99% yield, 96% ee
OH
HOTf
HO
OH
OH
OH
MeOH
rt, 24 h
2
Me
Me
2
O
O
14
93% yield, 99% ee
(–)-bifurcadiol
IV
80%
Br
[b]
(
)
3q
, 42 h
3r
3s
, 32 h
98% yield, 98% ee
ORTEP of
, 32 h
3q
94% yield, 90% ee
93% yield, 99% ee
Scheme 4. Synthetic route to (–)-bifurcadiol (IV).
(CCDC 1969342)
OH
OH
OH
*
OH
89% yield with 99% ee (Scheme 3). Finally, the removal of the
protecting group gave (–)-rosiridol (III) in 85% yield. Based on
S
S
Me
3t
3u
3v
, 28 h
97% yield, 96% ee
3w
, 32 h
(–)-
, 32 h
, 32 h
the reported S-configuration of III 11c
alcohol must be consequently also S-configured. Therefore,
the C–C bond formation between alkenyl aldehyde and
,
the stereogenic center in
96% yield, 99% ee
94% yield, 99% ee
93% yield, 93% ee
OH
*
OH
*
OH
*
9
OH
*
8
2
(prenylation) must have occurred from the aldehyde’s Re-face;
interestingly, this would be opposite to the case of aromatic
aldehydes (Si-face attack; cf. Scheme 2). Compared with the
reported stoichiometric methods,11 the present synthesis is
shorter and the stereogenic center was formed by asymmetric
catalysis. Encouraged by this success, a short total synthesis of
(–)-bifurcadiol (IV) was also achieved in five similar steps
starting from alcohol 10 (Scheme 4).11d Here, the precursor to
IV, homoprenyl alcohol 14, was formed under the optimized
conditions in 93% yield with 99% ee (Scheme 4); the absolute
configuration of the created stereogenic center in 14 was
[b]
3aa
, 39 h
(–)-
3x
, 32 h
(–)-
94% yield, 98% ee
3y
, 32 h
(–)-
96% yield, 84% ee
3z
, 32 h
(–)-
96% yield, 89% ee
94% yield, 84% ee
[a]
Reaction conditions (unless otherwise specified): 1 (0.10 mmol), 2 (0.15
mmol), (R)-4a (10 mol%), 4Å MS (25 mg), solvent (0.3 mL); yield of isolated
product; ee values were determined by chiral HPLC analysis. [b] The reaction
was performed in DCM at ‒78 oC.
Next, we focused on applying this asymmetric catalysis method to
the total synthesis of the natural products (–)-rosiridol (III) and (–)-
bifurcadiol (IV). As mentioned before, the total synthesis of these
compounds was achieved through a critical asymmetric reduction of
the corresponding prenyl ketone using a stoichiometric amount of a
chiral reductant.11c,d Moreover, the construction of the prenyl ketone
determined as S by comparison with the earlier report on IV 11d
.
substrates required three steps: prenylation of aldehyde 8 (cf. Scheme Thus, it turns out that the enantiofacial discrimination using
3) or 13 (cf. Scheme 4); oxidation of the resulting alcohol to the
corresponding ketone; asymmetric reduction. Such approach is
arguably more tedious and less sustainable than a direct catalytic
asymmetric prenylation of 8 or 13. With this in mind, we synthesized
alkenyl aldehyde 8 (Scheme 3). Distinct from the reported
alkenyl aldehydes is opposite to the one using aromatic
aldehydes.
In summary, we have established the first example of highly
enantioselective general aldehyde prenylation16 controlled by a
synthesis,11c we installed a trityl (Tr) protecting group on primary chiral phosphoric acid catalyst.
A
broad range of
alcohol 5 in 96% yield. The resulting ether 6 underwent standard
allylic oxidation to form alcohol 7 in 40% yield. Subsequent
oxidation of allylic alcohol 7 using MnO2 gave substrate 8 in 85%
yield. The catalytic asymmetric prenylation of 8 using 2 was carried
out under the optimized conditions to form homoprenyl alcohol 9 in
enantioenriched aryl, heteroaryl, aryl-substituted alkenyl, as well
as primary and secondary aliphatic homoprenyl alcohols have
been constructed regioselectively in high yields with excellent
asymmetric induction. The synthetic pathways to the two natural
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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9 For examples of racemic synthesis, see: (a) R. E. Estévez, J. Justicia,
products (–)-rosiridol and (–)-bifurcadiol were streamlined by
virtue of this catalytic asymmetric prenylation method. Further
B. Bazdi, N. Fuentes, M. Paradas, D. Choquesillo-VLieawzaArrttiecl,e JO.nlMine.
DOI: 10.1039/D0CC00367K
García-Ruiz, R. Robles, A. Gansäuer, J. M. Cuerva and J. E. Oltra,
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Jakoby, A. J. Mota, C. Kube, J. Justicia, J. M. Cuerva and A.
Gansäuer, Chem. Commun., 2014, 50, 2211; (g) N. D. Bartolo and
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applications of the
asymmetric reactions will be reported in due course.
α,α-dimethyl allyl boronic ester in other
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Y.-Y.H. gratefully acknowledges the financial support for this
investigation from the National Natural Science Foundation of China
(21772151), and Natural Science Foundation of Hubei Province
(2018CFA084).
10 (a) J. Nokami, K. Nomiyama, S. Matsuda, N. Imai and K. Kataoka,
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