Asymmetric sharpless dihydroxylation reaction of chiral bishomoallylic alcohols: Application to the synthesis of the C1-C10-C5 fragment of FR225654

Article abstract of DOI:10.1055/s-0033-1340164

Toward the synthesis of FR225654, an antidiabetic natural product, the Sharpless asymmetric dihydroxylation of chiral bishomoallylic alcohols, never reported in the literature, was examined. Employing the pyrimidine class of ligands, a high level of matched diastereoselectivity was obtained. An application to the stereoselective synthesis of the C1-C10-C5 fragment of FR225654 was performed. Georg Thieme Verlag Stuttgart · New York.

Full text of DOI:10.1055/s-0033-1340164

LETTER
▌2581
lAettserymmetric Sharpless Dihydroxylation Reaction of Chiral Bishomoallylic Al-
cohols: Application to the Synthesis of the C1–C10–C5 Fragment of FR225654
Synthesis of the C1–C10–C5 Fragment of FR225654
Shabbair Mohammad,a Sabrina Dhambri,a Didier Gori,b Carine Vaxelaire,a Geoffroy Sorin,a Janick Ardisson,a
Marie-Isabelle Lannou*a
a
CNRS UMR 8638, Faculté de Pharmacie, Université Paris Descartes, 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France
Fax +33(1)43291403; E-mail: marie-isabelle.lannou@parisdescartes.fr
b
ICMMO, UMR 8182, Bât. 410, Université Paris-Sud 11, 15 rue Georges Clemenceau, 91405 Orsay Cedex, France
Received: 31.07.2013; Accepted after revision: 02.09.2013
We envisioned to develop a general and efficient stereose-
Abstract: Toward the synthesis of FR225654, an antidiabetic natu-
lective method for synthesizing this unit by means of
ral product, the Sharpless asymmetric dihydroxylation of chiral
Sharpless asymmetric dihydroxylation (SAD)3 of the cor-
bishomoallylic alcohols, never reported in the literature, was exam-
ined. Employing the pyrimidine class of ligands, a high level of
responding chiral bishomoallylic alcohol 5 (Scheme 2).4,5
matched diastereoselectivity was obtained. An application to the
stereoselective synthesis of the C1–C10–C5 fragment of FR225654
reaction, prior interesting works have been reported.6
was performed.
In the context of a substrate-directed dihydroxylation
However, to our knowledge, no publication reports the
Key words: stereoselective synthesis, natural products, dihydroxy-
SAD reactions of such chiral olefins. In this context,
lation, diols, diastereoselectivity
Corey has evidenced that the combined use of the p-me-
thoxybenzoate protecting group and the noncommercial
As part of a screening program searching for new antidia-
OH
betic agents, FR225654 (1) was isolated from the culture
16
broth of Phoma sp. no. 00144.1 This trans-decalone selec-
tively inhibited gluconeogenesis of rat primary hepato-
cytes and had significant hypoglycemic effects in several
in vivo mouse models.
13
O
H
2'
5'
6
O
HO2C
11
4
1
14
OH
10
8
HO
O
H
FR225654 (1)
We have been interested in developing a synthesis of this
natural product from triene 2 by means of an intramolec-
ular Diels–Alder reaction (Scheme 1). Triol 4 was chosen
as the starting material for the synthesis of the central part
C1–C10–C5 (3).
O
Sonogashira coupling
HWE olefination
HO
14
IMDA
HO
13
5
3
1
OH
17
10
11
8
O
2
It is interesting to note that this structural motif, 2,4-di-
methylpentane-1,2,5-triol (4), is often found in biological-
ly active natural products (macrolide antibiotics, etc.) and
synthetic intermediates of organic substances (Figure 1).2
PG
HO
HO
HO
O
OPG
1
10
8
9
5
5
4
3
Scheme 1 Retrosynthetic analysis of FR225654 (1)
HO
HO
OPG
4
O
O
O
H
OH
HO
OH
O
H
OH
HO
OH
O
OR1
O
OH
O
OR1
OR2
H
O
H
O
OR1
O
O
erythronolide A
lankanolide
lankamycin
ent-homoabyssomicin A
Figure 1 Biologically active natural products including structural motif 4
SYNLETT 2013, 24, 2581–2585
Advanced online publication: 18.10.2013
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
DOI: 10.1055/s-0033-1340164; Art ID: ST-2013-B0724-L
© Georg Thieme Verlag Stuttgart · New York

2582
S. Mohammad et al.
LETTER
As this study has been carried out in the context of total
synthesis, the choice of the alcohol protecting group is
critical and unfortunately, p-methoxybenzoate and benzyl
groups were unsuitable. PMB and PMP groups, on the
other hand, gave satisfactory results. For this purpose, we
examined the reactivity of olefins (R)- and (S)-12
(OPMB) and (R)- and (S)-13 (OPMP) using (DHQ)2 or
(DHQD)2 ligands and PHAL, AQN, or PYR as linkers.
Reactions were performed under stronger conditions (i.e.
1 mol% K2OsO4·2H2O) in order to selectively access tri-
ols 14–17 and ent-14–17 (Scheme 4).10 The data for these
experiments are summarized in Tables 1 and 2.
HO
SAD
OPG
HO
OPG
4
55
Scheme 2 Synthesis of chiral bishomoallylic alcohol 4 by means of
the SAD reaction of olefin 5
(DHQD)2PYDZ-AntCl ligand permit to reach high enan-
tiomeric excesses in the SAD of achiral bishomoallylic al-
cohols by enhancing aryl–aryl contacts.7 Hence, synthesis
of diol 7 was achieved in high yield and enantiomeric ex-
cess from olefin 6 (Scheme 3). More surprisingly, Pa-
quette reported the dihydroxylation of achiral benzyl ether
8 derived from 4-methylpent-4-en-1-ol using commercial
(DHQ)2PHAL as ligand to access diol 9 in high yield and
selectivity.8a,b In contrast, results are markedly lower for
chiral substrates in double diastereoselection. In 2008,
Kalesse described the SAD reaction of the PMB ether of
(S)-2-methyl-4-pentenol (S)-10 with commercial AD-
mix-α to provide diol anti-11. The reaction sluggishly
proceeded within three days and delivered the diol in a
poor 4:1 diastereomeric ratio.9
The synthesis of SAD precursors (R)- and (S)-12 (OPMB)
was accomplished, respectively, from known (S)- and (R)-
iodides 1811 through a Cu(I)-catalyzed cross-coupling re-
action with 2-propenylmagnesium bromide.12 Cleavage of
the PMB ether and subsequent protection of the hydroxyl
function as its PMP ether provided the corresponding (R)-
and (S)-13 olefins (Scheme 5).13,14
b,c
a
OPMP
OPMB
I
OPMB
(S)-12
(R)-12
(R)-18
(S)-18
(S)-13
(R)-13
K2OsO4⋅2H2O (1 mol%)
(DHQD)2PYDZ-AntCl (1 mol%)
Corey
K2CO3 (3 equiv)
K3Fe(CN)6 (3 equiv)
Scheme 5 Synthesis of olefins 12 and 13. Reagents and conditions:
(a) CuI, H2C=C(Me)-MgBr, THF, –78 °C to r.t., 14 h, 95%; (b) DDQ,
CH2Cl2–H2O (20:1), 0 °C to r.t., 12 h, 72%; (c) Ph3P, PMPOH, DI-
AD, CH2Cl2, 0 °C to r.t., 3 h, 98%.
HO
4 h, 0 °C
PMP
PMP
O
HO
O
6
90%, ee 99%
7
O
O
K2OsO4⋅2H2O (0.4 mol%)
(DHQ)2PHAL (1 mol%)
K2CO3 (3 equiv)
K3Fe(CN)6 (3 equiv)
7 h, 0 °C
We initiated our investigation by carrying out the osmy-
lation of (R)- and (S)-12 in the absence of chiral ligands
(Table 1, entries 1 and 8);14 however, these reactions only
displayed a low diastereoselectivity. The SAD reaction of
(R)- and (S)-12 was then studied (Table 1, entries 2–7 and
9–14). It was found that pyrimidine derivatives
(DHQD)2PYR or (DHQ)2PYR were the ligands of choice
in matched reactions to afford 14 or ent-14 with high yield
and stereoselectivity (dr = 96:4 and 91:9; Table 1, entries
6 and 14).
Paquette
HO
HO
OBn
OBn
98%, ee >95%
9
8
commercially available AD-mix α
K2OsO4⋅2H2O (0.2 mol%)
(DHQ)2PHAL 1 mol%]
4 d, 0 °C
Kalesse
HO
HO
OPMB
(S)-10
OPMB
78%, ee 60%
However, in mismatched reactions, very low diastereose-
lection was observed to provide 16 or ent-16, regardless
the ligand, that is, (DHQ)2 or (DHQD)2 and the linker
(PHAL, AQN, or PYR) (Table 1, entries 3, 5, 7, 9, 11 and
13): in all cases, it appears that overriding the intrinsic dia-
stereofacial preference of the olefin substrate is difficult
for the dihydroxylation reagent.
anti-11
Scheme 3 Synthesis of diols 7, 9, and anti-11 by the SAD reaction
We describe here the results of our study to optimize the
SAD reaction of chiral olefin 5 with the aim of a stereose-
lective preparation of triol 4. The experiments were per-
formed to assess the relative ability of different ligands in
the context of matching and mismatching.
HO
HO
HO
HO
OPG
OPG
OPG
K2OsO4⋅2H2O (1 mol%)
Ligand (2.5 mol%)
(R)-12 PG = PMB
(R)-13 PG = PMP
14 PG = PMB
15 PG = PMP
16 PG = PMB
17 PG = PMP
K2CO3 (3 equiv)
HO
HO
HO
K3Fe(CN)6 (3 equiv)
MeSO2NH2 (1 equiv)
t-BuOH–H2O (1:1), 0 °C
OPG
HO
OPG
OPG
(S)-12 PG = PMB
(S)-13 PG = PMP
ent-16 PG = PMB
ent-17 PG = PMP
ent-14 PG = PMB
ent-15 PG = PMP
Scheme 4 Synthesis of triols 14–17 and ent-14–17
Synlett 2013, 24, 2581–2585
© Georg Thieme Verlag Stuttgart · New York

LETTER
Synthesis of the C1–C10–C5 Fragment of FR225654
2583
Table 1 SAD of Olefins (R)-12 and (S)-12 (OPMB)
Entry
Substrate
Ligand (2.5 mol%)
Yield (%)a
Time (h)
drb
1
(R)-12
(R)-12
(R)-12
(R)-12
(R)-12
(R)-12
(R)-12
(S)-12
(S)-12
(S)-12
(S)-12
(S)-12
(S)-12
(S)-12
–
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
12
4
14/16 57:43
14/16 54:46
14/16 23:73
14/16 73:27
14/16 43:57
14/16 96:4
14/16 33:67
2
(DHQD)2-PHAL
(DHQ)2-PHAL
(DHQD)2-AQN
(DHQ)2-AQN
(DHQD)2-PYR
(DHQ)2-PYR
–
3
12
12
12
12
12
12
3
4
5
6
7
8
ent-14/ent-16 57:43
ent-14/ent-16 45:55
ent-14/ent-16 59:41
ent-14/ent-16 39:61
ent-14/ent-16 73:23
ent-14/ent-16 35:65
ent-14/ent-16 91:9
9
(DHQD)2-PHAL
(DHQ)2-PHAL
(DHQD)2-AQN
(DHQ)2-AQN
(DHQD)2-PYR
(DHQ)2-PYR
10
3
11
12
12
2
12
13
14
12
a Isolated yield.
b Determined by HPLC.
Considering observations made by Corey,7 a variation of OPMP ethers (R)- and (S)-13 to yield 15 or 17 and ent-15
the alcohol protecting group from PMB to PMP was envi- or ent-17.
sioned in order to modify the catalyst–substrate interac-
tion while keeping favorable π-interactions, SAD
experiments were thus performed on the corresponding
however, it is interesting to note a remarkable increase of
Similar results were observed in the context of matched
and mismatched pairing (Table 2, entries 2–7 and 9–14);
Table 2 SAD of Olefins (R)-13 and (S)-13 (OPMP)
Entry
Substrate
Ligand (2.5 mol%)
Yield (%)a
Time (h)
drb
1
(R)-13
(R)-13
(R)-13
(R)-13
(R)-13
(R)-13
(R)-13
(S)-13
(S)-13
(S)-13
(S)-13
(S)-13
(S)-13
(S)-13
–
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
quant.
12
3.5
3.5
3.5
3.5
1.5
1.5
12
3
15/17 55:45
2
(DHQD)2-PHAL
(DHQ)2-PHAL
(DHQD)2-AQN
(DHQ)2-AQN
(DHQD)2-PYR
(DHQ)2-PYR
–
15/17 55:45
3
15/17 41:59
4
15/17 72:28
5
15/17 34:66
6
15/17 92:8
7
15/17 37:63
8
ent-15/ent-17 58:42
ent-15/ent-17 45:55
ent-15/ent-17 62:38
ent-15/ent-17 34:66
ent-15/ent-17 74:26
ent-15/ent-17 36:64
ent-15/ent-17 89:11
9
(DHQD)2-PHAL
(DHQ)2-PHAL
(DHQD)2-AQN
(DHQ)2-AQN
(DHQD)2-PYR
(DHQ)2-PYR
10
3
11
3
12
3
13
2
14
2
a Isolated yield.
b Determined by HPLC.
© Georg Thieme Verlag Stuttgart · New York
Synlett 2013, 24, 2581–2585

2584
S. Mohammad et al.
LETTER
Table 3 SAD of (S)-10 and (R)-10 and Olefin 19
Entry
Substrate
Ligand (2.5 mol%)
Yield (%)a
Time (h)
drb
1
(S)-10
(S)-10
(R)-10
(R)-19
(R)-19
(DHQ)2-PHAL
(DHQ)2-PYR
(DHQD)2-PYR
–
90
3
5
anti-11/syn-11 81:19
anti-11/syn-11 91:9
2
87
3
80
7
anti-ent-11/syn-ent-11 96:4
anti-20/syn-20 52:48
anti-20/syn-20 90:10
4
quant.
quant.
12
5
5
(DHQD)2-PYR
a Isolated yield.
b Determined by HPLC.
the turnover rate. These conditions have also proven to be exceed 74% and 84% (Table 4, entries 3 and 6). Notewor-
very useful for the SAD of Kalesse olefins (S)-10 and (R)- thy, both starting materials 21 (OPMB) and 22 (OPMP)
10 (Table 3).9 Ratio preferences of 91:9 and 96:4 were ob- were easily obtained from alcohol 20 (Scheme 7).
served in the reaction employing PYR as linker to yield 11
and ent-11 both anti (Table 3, entries 2 and 3).
K2OsO4⋅2H2O (1 mol%)
ligand (2.5 mol%)
K2CO3 (3 equiv)
HO
A similar set of experiments was carried out on olefin (R)-
19 to yield diol 20 in high selectivity in a matched pair
(Scheme 6, Table 3, entries 4 and 5).
OR
HO
OR
20 R = H
21 R = OPMB
22 R = OPMP
23 R = OPMB
24 R = OPMP
K3Fe(CN)6 (3 equiv)
MeSO2NH2 (1 equiv)
t-BuOH–H2O (1:1), 0 °C
As a final point, SAD reaction of achiral Paquette olefin 8
(OBn) was re-examined. However, in our hands, under
previously reported conditions,8a enantiocontrol was only
58% ee (Table 4, entry 1).
Scheme 7 Synthesis of diols 23 and 24
Finally, the SAD product 15 was easily transformed into
the desired fragment C1–C10–C5 (25) of FR225654, after
epoxidation, epoxide ring opening with trimethylsi-
lylacetylide, and deprotection (Scheme 8).15
Table 4 SAD of Olefins 8, 21, and 22
Entry Substrate Ligand
Yield
(%)a
Time erb
(h)
TMS
1
2
3
4
5
6
7
8
21
21
21
22
22
22
(DHQ)2-PHAL
quant.
48a
1
9 79:21
HO
HO
a–c
HO
1
OPMP
OH
10
(DHQD)2-PHAL quant.
23 83:17
23 87:13
23 85:15
24 84:16
24 92:8
8
9
5
5
15
25
(DHQD)2-AQN
(DHQD)2-PYR
quant.
quant.
2
Scheme 8 Synthesis of fragment 25. Reagents and conditions:
(a) MsCl, LDA, THF, –10 °C, 3 h; (b) n-BuLi, BF3·OEt2, HCCSiMe3,
THF, –78 °C to r.t., 3 h, 70% (2 steps); (c) CAN, NaHCO3, MeCN–
H2O (4:1), 0 °C, 10 min, 75%.
2
(DHQD)2-PHAL quant.
1
(DHQD)2-AQN
(DHQD)2-PYR
quant.
quant.
2
1
24 85:15
In conclusion, this work presents an overview of the po-
tential of the SAD reaction as a tool for accessing 2,4-di-
methylpentane-1,2,5-triol motifs or to similar systems
often found in biologically active natural products. To this
aim, the performance of the SAD reaction of chiral PMB
or PMP ether of bishomoallylic alcohols was evaluated in
double diastereoselection. If limitations appeared when
reactions are performed under mismatched conditions, on
the contrary very high levels of matched diastereoselec-
tivity were obtained employing the pyrimidine class of li-
a Isolated yield.
b Determined by HPLC.
Based on our work, SAD reaction of achiral olefins 21
(OPMB) and 22 (OPMP) was then examined under stron-
ger conditions. Surprisingly, slightly better results were
obtained with AQN rather than with PYR spacer; how-
ever, the enantiomeric excess of diols 23 and 24 could not
K2OsO4⋅2H2O (1 mol%)
ligand (2.5 mol%)
K2CO3 (3 equiv)
OH
a
OPMB
HO
OPMB
(S)-18
(R)-19
K3Fe(CN)6 (3 equiv)
MeSO2NH2 (1 equiv)
t-BuOH–H2O (1:1), 0 °C
anti-20
Scheme 6 Synthesis of diol 20. Reagents and conditions: (a) CuI, Me2C=CH-MgBr, THF, –78 °C to r.t., 12 h, 95%.
Synlett 2013, 24, 2581–2585
© Georg Thieme Verlag Stuttgart · New York

LETTER
Synthesis of the C1–C10–C5 Fragment of FR225654
2585
mixture of t-BuOH–H2O (10 mL) at 0 °C. The reaction
mixture was stirred at 0 °C and monitored by TLC. Upon
completion, the reaction mixture was quenched with solid
Na2SO3 (1.5 g), warmed to r.t., and stirred for an additional
60 min. The product was extracted with EtOAc, washed with
brine, dried over MgSO4, concentrated, and purified on silica
gel to afford an inseparable mixture of the required diol and
the corresponding diastereomer.
gands. Noteworthy, with the PMP protecting group, the
reaction rate is significantly increased. Finally, an effec-
tive application to the stereoselective synthesis of the
C1–C10–C5 fragment of FR225654 has been achieved.
Acknowledgment
Spectroscopic Data of Diol 14 (Major Isomer)
1H NMR (300 MHz, CDCl3): δ = 7.26 (d, J = 8.6 Hz, 2 H),
6.89 (d, J = 8.6 Hz, 2 H), 4.47 (s, 2 H), 3.80 (s, 3 H), 3.42
(dd, J = 4.2, 9.0 Hz, 1 H), 3.38 (d, J = 12.0 Hz, 1 H), 3.32 (d,
J = 12.0 Hz, 1 H), 3.21 (m, 1 H), 2.11 (m, 1 H), 1.68 (dd, J
= 7.8, 14.6 Hz, 1 H), 1.36 (dd, J = 3.3, 14.6 Hz, 1 H), 1.16 (s,
3 H), 0.93 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 159.1, 12 9.3, 113.7, 76.6, 72.8, 71.8, 70.9,
55.0, 4 4.3, 28.6, 23.5, 19.5 ppm.
We gratefully acknowledge MENRT for a fellowship awarded to
S.M.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.SnoIufproig
m
iotSrat
ungIifoop
r
t
References and Notes
Spectroscopic Data of Diol 16 (Minor Isomer)
1H NMR (300 MHz, CDCl3): δ = 7.26 (d, J = 8.6 Hz, 2 H),
6.89 (d, J = 8.6 Hz, 2 H), 4. 46 (s, 2 H ), 3.80 (s, 3 H), 3.48
(m, 1 H), 3.38 (d, J = 11.0 Hz, 1 H), 3.32 (d, J = 11.0 Hz, 1
H), 3.19 (m, 1 H), 1.95 (m, 1 H), 1.63 (dd, J = 6.0, 14.4 Hz,
1 H), 1.45 (dd, J = 4.8, 14.4 Hz, 1 H), 1.16 (s, 3 H), 0.95 (d,
J = 6 . 9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3) δ =
159.1, 129.3, 113.7, 76.4, 72.6, 71.8, 69.0, 55.0, 44.0, 29.1,
24.3, 19.3 ppm. IR (neat): ν = 3360, 2932, 1611, 1513, 1462,
1246, 1033, 819, 771 cm–1. ESI-HRMS: m/z calcd for
C15H24NaO4+ [MNa+]: 291.1567; found: 291.1570.
For spectroscopic data of all diols, see the Supporting
Information.
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(a) Heckrodt, T. J.; Mulzer, J. Synthesis 2002, 1857.
(b) Haslett, G. W.; Paterson, I. Org. Lett. 2013, 15, 1338.
(c) For the typical procedure and spectroscopic data of
substrates, see the Supporting Information.
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68, 3090. (b) Hareau, G. P.-J.; Koiwa, M.; Hikichi, S.; Sato,
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(13) For analytical data for 12 and 13, see the Supporting
Information.
(14) For the osmylation of (R)- and (S)-12 and (R)- and (S)-13 in
the absence of chiral ligands, see general procedure (ref. 10),
however, without ligand.
(15) Analytical Data for 25
1H NMR (400 MHz, CDCl3): δ = 4.28–4.01 (br s, 2 H), 3.56
(dd, J = 3.6, 10.5 Hz, 1 H), 3.27 (dd, J = 9.0, 10.5 Hz, 1 H),
2.40 (d, J = 16.8 Hz, 1 Hz), 2.33 (d, J = 16.8 Hz, 1 H), 1.93
(m, 1 H), 1.58 (m, 2 H), 1.28 (s, 3 H), 0.86 (d, J = 6.9 Hz, 3
H), 0.13 (s, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
103.7, 87.9, 71.7, 68.9, 47.3, 36.1, 31.8, 25.4, 19.6, 0.1 ppm.
IR (neat): ν = 3276, 2958, 2927, 2175, 1460, 1423, 1376,
1248, 1032, 758 cm–1. ESI-HRMS: m/z calcd for
C12H24NaO2Si+ [MNa+]: 251.1438; found: 251.1439. The
relative configuration of 25 was confirmed by NMR
experiments (NOESY analysis) of the corresponding γ-
lactone (Figure 2).
(7) Corey, E. J.; Noe, M. C.; Ting, A. Y. Tetrahedron Lett. 1996,
37, 1735.
(8) (a) Bondar, D.; Liu, J.; Müller, T.; Paquette, L. A. Org. Lett.
2005, 7, 1813. (b) In another paper, SAD of tert-
butyltrimethylsilyl ether protected 4-methylpent-4-en-1-ol
was reported, however, without mention of the ee of the
resulting diol: O’Connor, P. D.; Knight, C. K.; Friedrich, D.;
Peng, X.; Paquette, L. A. J. Org. Chem. 2007, 72, 1747.
(9) Lorenz, M.; Kalesse, M. Org. Lett. 2008, 10, 4371.
(10) Typical Procedure for the Sharpless Asymmetric
Dihydroxylation
H3C
O
H
H
O
NOE
H
H3C
K2CO3 (415 mg, 3 mmol), K3Fe(CN)6 (1.18 g, 3 mol),
K2OsO2(OH)4 (4 mg, 0.01 mmol), ligand (0.025 mol), and
MeSO2NH2 (95 mg, 1 mmol) were added to a vigorously
magnetically stirred solution of olefin (1 mmol) in a 1:1
TMS
Figure 2
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Synlett 2013, 24, 2581–2585

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