A five-step formal synthesis of (-)-Jaspine B

Article abstract of DOI:10.1016/j.tetlet.2011.09.045

A new application of the sequential hydrolysis-oxidation-Wittig olefination (SHOWO) protocol to a D-glu-cose derivative, and an anomeric deoxygenation reaction of a xylo-D-furanose derivative is presented for the five-step formal synthesis of (-)-Jaspine

Full text of DOI:10.1016/j.tetlet.2011.09.045

Tetrahedron Letters 52 (2011) 6370–6371
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Tetrahedron Letters
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A five-step formal synthesis of (À)-Jaspine B
Silvano Cruz-Gregorio, Cristhian Espinoza-Rojas, Leticia Quintero, Fernando Sartillo-Piscil
⇑
Centro de Investigación de la Facultad de Ciencias Químicas, BUAP 14 Sur Esq. San Claudio, San Manuel 72570, Puebla, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
A new application of the sequential hydrolysis-oxidation-Wittig olefination (SHOWO) protocol to a
D-glu-
Received 16 August 2011
Revised 8 September 2011
Accepted 11 September 2011
Available online 16 September 2011
cose derivative, and an anomeric deoxygenation reaction of a xylo-
the five-step formal synthesis of (À)-Jaspine B.
D-furanose derivative is presented for
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
SHOWO protocol
Jaspine B
Chiral pool
Since the publication of the original report on the isolation of
Jaspine B from the Okinawa marine sponge Pachastrissa sp. by Higa
and coworkers1 the organic synthetic community has been deeply
interested to develop the most concise total synthesis of this anti-
tumor compound.2 Although some asymmetric total syntheses
have been reported, in which are included: Sharpless asymmetric
epoxidation,2f Sharpless asymmetric dihydroxylation,2k or Davies
conjugate additions of homochiral lithium amides,2k,m the chiron
approach represents probably the better way for preparing Jaspine
B and even other biologically active Jaspines (Fig. 1).3
5 in quantitative yield (98%); then 5 was submitted to SHOWO pro-
tocol,7 which consists of one-pot three-step processes: hydrolysis of
the 5,6-O-isopropylidene group/oxidative cleavage of the formed
5,6-diol and Wittig olefination, to afford compound 6 in only 6 h
and 86% yield. It is important to note that, following the traditional
procedure for this type of chain elongation (aqueous hydrolysis/
NaIO4 5,6-diol cleavage and Wittig olefination), two days are needed
and lower overall yields are obtained. Having the compound 6 in
hand (major Z-olefine isomer), the formation of the tetrahydrofuran
ring (8) was achieved in a straightforward manner via nucleophilic
substitution reaction at the anomeric position of 6 under Robins
conditions (Et3SiH/BF3ÁOEt2).6,8 Finally, the (À)-Jaspine B precursor
7 was obtained via the eventual formation of the triflate group with
trifluoromethanesulfonic chloride and DMAP followed by a S2N dis-
placement reaction with sodium azide in the presence of tetrabutyl-
ammonium fluoride (Scheme 2).9 It is important to note that this
procedure is effective for the azide group introduction and avoids
the formation of the elimination products.4
Among the wide repertory of (+)/(À)-Jaspine B and 2-epi-(+)/(À)-
JaspineBtotalsyntheses, wherethechironapproachisused, wereal-
ized that the use of both D-glucose (1) and D-xylose offers more
advantages than any other carbohydrate. Two of those advantages
are: rapid construction of the tetrahydrofuran ring and easy installa-
tion of the long chain. In this regard, Chandrasekhar and coworkers
obtained the truncated (+)-Jaspine B in 12 steps from L-xylose 2 fea-
turing Wittig olefination of aldehyde 3 for chain elongation, and
reductive removal of the methoxy group of 4 with triethylsilane
for the formation of the tetrahydrofuranose ring.4
Natural Jaspines B
In this sense, we realized that it could be feasible to develop a
highly efficient and concise formal synthesis of (À)-Jaspine B if we
only applied the sequential hydrolysis-oxidation-Wittig olefination
(SHOWO) protocol5 to the DAG derivative 5 for chainelongation, and
O
O
C14H29
C14H29
H2N
H2N
2-epi-(+)-Jaspine B
OH
OH
the Robins anomeric deoxygenation6 to 1,2-O-isopropylidene-
a-D-
(+)-Jaspine B
xylofuranosederivative6 fortheconstructionofthetetrahydrofuran
moiety (Scheme 1).
In this sense, we started with the benzylation of the hydroxyl
group at C-3 of DAG under standard conditions (BnBr/NaH) to afford
Unnatural Jaspines B
O
O
C14H29
C14H29
H2N
2-epi-(-)-Jaspine B
H2N
(-)-Jaspine B
OH
OH
⇑
Corresponding author. Tel.: +52 222 2295500x7391; fax: +52 222 2295500.
E-mail address: fsarpis@siu.buap.mx (F. Sartillo-Piscil).
Figure 1. Natural and unnatural Jaspines B with cytotoxic activity.
0040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2011.09.045

S. Cruz-Gregorio et al. / Tetrahedron Letters 52 (2011) 6370–6371
6371
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Fernandez, E. M.; Scott, P. M.; Smith, A. D.; Thomson, J. E. Org. Biomol. Chem.
2008, 6, 1665; (n) Passiniemi, M.; Koskinen, A. M. P. Tetrahedron Lett. 2008, 49,
980; (o) Venkatesan, K.; Srinivasan, K. V. Tetrahedron: Asymmetry 2008, 19, 209;
(p) Enders, D.; Terteryan, V.; Palecek, J. Synthesis 2008, 2278; (q) Ichikawa, Y.;
Matsunaga, K.; Masuda, T.; Kotsuki, H.; Nakano, K. Tetrahedron 2008, 64, 11313;
(r) Reddipalli, G. S.; Venkataiah, M.; Mishra, M. K.; Fadnavis, N. W. Tetrahedron:
Asymmetry 2009, 20, 1802; (s) Inuki, S.; Yoshimitsu, Y.; Oishi, S.; Fujii, N.; Ohno,
H. Org. Lett. 2009, 11, 4478; (t) Inuki, S.; Yoshimitsu, Y.; Oishi, S.; Fujii, N.; Ohno,
H. J. Org Chem. 2010, 75, 3831; (u) Yoshimitsu, Y.; Inuki, S.; Oishi, S.; Fujii, N.;
Ohno, H. J. Org. Chem. 2010, 75, 3843; (v) Urano, H.; Enomoto, M.; Kuwahara, S.
Biosci., Biotechnol., Biochem. 2010, 74, 152; (w) Salma, Y.; Ballereau, S.; Maaliki,
C.; Ladeira, S.; Andrieu-Abadie, N.; Genison, Y. Org. Biomol. Chem. 2010, 8, 3227;
(x) Passiniemi, M.; Koskinen, A. M. P. Org. Biomol. Chem. 2011, 9, 1774; (y)
Llaveria, J.; Diaz, Y.; Matheu, M. I.; Castillon, S. Eur. J. Org. Chem. 2011, 1514; (z)
Sanchez-Eleuterio, A.; Quintero, L.; Sartillo-Piscil, F. J. Org. Chem. 2011, 76, 5466;
For a review, see: (aa) Abraham, E.; Davies, S. G.; Roberts, P. M.; Russell, A. J.;
Thomson, J. E. Tetrahedron: Asymmetry 2008, 19, 1027.
Chandrasekhar synthesis of truncated (+)-Jaspine B
O
O
O
OH
5 steps
HO
O
O
O
Wittig
BnO
O
HO
OH
BnO
O
3
2
3 steps
O
O
O
OMe
N3
2 steps
HO
NH2
BnO
N3
BnO
4
Truncated (+)-Jaspine B
Current approach to (-)-Jaspine B
anomeric
deoxygenation
C14H27
O
C14H29
O
C14H27
O
refs.
O
O
BnO
HO
(-)-Jaspine B
BnO
NH2
N3
6
7
O
O
SHOWO
O
O
3. Twenty seven synthesis of Jaspine B and diastereoisomers, and 22 synthesis
involved the use of the Chiral Pool.
4. Chandrasekhar, S.; Tiwari, B.; Prakash, S. J. ARKIVOK 2006, 155.
O
O
O
O
5. For examples of the SHOWO protocol in synthesis: (a) Sartillo-Piscil, F.; Vargas,
M.; Anaya de Parrodi, C.; Quintero, L. Tetrahedron Lett. 2003, 44, 3919; (b) Reddy,
L. V. R.; Swamy, G. N.; Shaw, A. K. Tetrahedron: Asymmetry 2008, 19, 1372; (c)
Ramirez, E.; Meza-Leon, R.; Quintero, L.; Sartillo-Piscil, F. Tetrahedron Lett. 2010,
51, 2178; (d) Sidnei, M.; Ligeour, T. C.; Caroline, L.; Christine, G.; Delphine, J.;
Emanuelle, D.; Francoise, D. Green Chem. 2011, 13, 1812; (e) Venkat, R. P.; Vikas,
B.; Brijesh, K.; Shaw, A. K. Eur. J. Org. Chem. 2011, 1575.
HO
O
BnO
O
1
5
DAG
Scheme 1. Chandrasekhar synthesis of truncated (+)-Jaspine B (12 steps) and
current approach for (À)-Jaspine B.
6. Ewing, G. J.; Robins, M. J. Org. Lett. 1999, 1, 635.
7. A solution of 5 (2.0 g, 5.7 mmol) and periodic acid (1.55 g, 6.8 mol) in 80 mL of dry
ethyl acetate was stirred for 2 h, whereby a solid formed that was separated by
filtration. Evaporation under reduced pressure afforded a colorless syrup, which
was dissolved in 50 mL of THF. This solution was added dropwise to the solution of
phosphorus ylide previously prepared [tridecyltriphenylphosphonium bromide
(3.6 g, 6.84 mmol) in 150 mL of dried THF under an atmosphere of argon, the
mixture was cooled at 0 °C and n-butyllithium was added dropwise (5.13 mL,
8.2 mmol of THF solution 1.6 M); the reaction mixture was stirred for 30 min]. The
resulting reaction mixture was stirred at for 4 h 0 °C. The reaction was stopped by
the addition of 50 mL of water. Extracted with ethyl acetate (3 Â 50 mL), dried the
combined organic phase over Na2SO4 and concentrated under reduced pressure.
The residue was purified by column chromatography to yield 2.18 g of 6 (86%
O
O
O
O
O
BF3 OEt2
O
R'
R'
O
H5IO6
Ph3 CHR'
86%
Et3SiH
84%
BnO
BnO
O
OH
8
6
P
RO
O
1. CF3SO2Cl/DMAP
2. NaN3/TBAF
69% from 8
R' = C12H25
1: R = H
5: R = Bn
BnBr/NaH
98%
reductions of double bond
and azide group,
and debenzylation
in one pot
O
C14H29
O
R'
BnO
yield) as a Z/E mixture (9:1, respectively). [
a]
D = À68.3 (c 1.0, CHCl3), 1H NMR
N3
7
HO
NH2
refs. 2d, 2e, 2g, 4
(400 MHz, CDCl3) d: 0.89 (t, J = 7.2 Hz, 3H), 1.25 (m, 20H), 1.32 (s, 3H), 1.52 (s, 3H),
2.07 (m, 2H), 3.83 (d, J = 2.8 Hz 1H), 4.55 (d, J = 12.0 Hz, 1H), 4.62 (d, J = 3.6 Hz, 1H),
4.64 (d, J = 12.0 Hz, 1H), 4.94 (dd, J = 7.6, 3.2 Hz, 1H), 5.69 (m, 2H), 5.95 (d,
J = 3.6 Hz, 1H), 7.31 (m, 5H). 13C NMR (100 MHz, CDCl3) d: 14.1, 22.6, 23.2, 26.1,
26.2, 26.8, 26.9, 28.0, 29.1, 29.3, 29.4, 29.43, 29.5, 29.6, 31.9, 41.5, 71.9, 75.8, 83.0,
83.3, 104.6, 111.3, 123.4, 127.4, 127.7, 128.3, 135.2, 137.6. HRMS-FAB mode, calcd
for C28H44O4: 444.3240; found 444.3244.
(-)-Jaspine B
Scheme 2. Five-steps formal synthesis of (À)-Jaspine B.
In summary, we have described here, a five-step formal synthe-
sis of (À)-Jaspine B (six-step total synthesis if we used the general
one-pot reduction and deprotection protocol widely reported),
which represents the most concise route to (À)-Jaspine B. Addi-
tionally, in this Letter it has been shown (once again) that the SHO-
WO protocol is an effective and powerful tool in the synthetic
scenario for chain elongation processes.
8. To a solution of 6 (0.5 g, 1.12 mmol) in CH2Cl2 (50 mL) at 0 °C were added trietyl
silane (0.71 mL, 4.48 mmol) and BF3ÁEt2O (0.16 mL, 1.34 mmol). The reaction
mixture was stirred at ambient temperature for 2 h, before to add an aqueous
saturated solution of NaHCO3 (15 mL) and CH2Cl2 (40 mL). The aqueous layer
was extracted with CH2Cl2 (3 Â 50 mL), and the combined organic phase was
dried over Na2SO4 and concentrated under reduced pressure. The resulting
residue was purified by flash chromatography to afford 0.37 g of 8 in (84% yield),
as a white solid, mp = 45 °C; [
a
]
D = À64.2 (c = 1.0, CHCl3) 1H NMR (400 MHz,
CDCl3) d: 0.88 (t, J = 6.8 Hz, 3H), 1.25 (m, 20H), 2.10 (m, 2H), 3.67 (dd, J = 10.0,
1.6 Hz, 1H), 3.78 (dd, J = 4, 1.2 Hz, 1H), 4.20 (dd, J = 10.0, 4.4 Hz, 1H), 4.40 (b, 1H),
4.60 (s, 2H), 4.83 (dd, J = 8.0, 4.0 Hz, 1H), 5.68 (m, 2H), 7.31 (m, 5H). 13C NMR
(100 MHz, CDCl3) d: 14.1, 22.7, 27.9, 29.3, 29.4, 29.5, 29.6, 29.7, 31.9, 72.2, 73.4,
75.8, 75.9, 85.6, 124.5, 127.4, 127.7 128.4, 134.9, 137.9. HRMS-FAB mode, calcd
for C25H40O3: 388.2977; found 388.3010.
Acknowledgment
We thank CONACyT for financial support (Grant number:
62203).
9. Trifluoromethanesulfonyl chloride (0.68 mL, 6.45 mmol) was added dropwise to
a stirred solution of 8 (0.5 g, 1.29 mmol) dissolved in CH2Cl2 (6 mL) at 0 °C. After
10 min, DMAP (0.18 g, 1.5 mmol) was added to the stirred solution at the same
temperature and allowed to react for 24 h. The reaction mixture was
concentrated under reduced pressure and washed successively with hexane
(3 Â 5 mL). The organic layer was concentrated and the residue was dissolved in
DMF (2.5 mL), and NaN3 (0.168 g, 2.58 mmol) and tetrabutylammonium fluoride
1.0 M (1.29 mL, 1.29 mmol) were added. The resulting reaction mixture was
stirred at rt for 24 h. The reaction mixture was concentrated under reduced
pressure and the residue was purified by column chromatography on silica gel
References and notes
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to obtain 0.37 g of 7 (69% yield) as a syrup. [
a]
D = À80.1 (c = CHCl3). 1H NMR
(400 MHz, CDCl3) d: 0.88 (t, J = 6.8 Hz, 3H), 1.25 (m, 20H), 2.08 (m, 2H), 3.95 (m,
3H), 4.10 (t, J = 4.8 Hz, 1H), 4.64 (d, J = 12.0 Hz, 1H), 4.69 (d, J = 12.0 Hz, 1H), 4.70
(m, 1H), 5.70 (m, 2H), 7.35 (m, 5H). 13C NMR (100 MHz, CDCl3) d: 14.11, 22.7,
27.8, 29.3, 29.34, 29.5, 29.7, 31.9, 61.6, 68.7, 73.3 75.8, 80.4, 124.9, 127.8, 127.9,
128.4, 135.2, 137.4.