3
Table 1: Reduction of ketone functionality in 7.
R.; Bond, R. W.; McPhail, A. T. Tetrahedron Lett. 2000, 41,
351–1354.
1
S. No.
Reagent
Reaction
1/2
Yield
9.
(a) Mohapatra, D. K.; Bhimireddy, E.; Krishnarao, P. S.; Das, P. P.;
Yadav, J. S. Org. Lett. 2011, 13, 4, 744–747. (b) Yadav, J. S.;
Pattanayak, M. R.; Das, P. P.; Mohapatra, D. K. Org. Lett. 2011, 13,
7, 1710–1713. (c) Mohapatra, D. K.; Maity, S.; Rao, T. S.; Yadav, J.
S.; Sridhar, B. Eur. J. Org. Chem. 2013, 2859–2863. (d) Pradhan, T.
R.; Das, P. P.; Mohapatra, D. K. Synthesis 2014, 46, 1177–1184. (e)
Mohapatra, D. K.; Krishnarao, P. S.; Bhimireddy, E.; Yadav, J. S.
Synthesis 2014, 46, 1639–1647. (f) Reddy, D. S.; Padhi, B.;
Mohapatra, D. K. J. Org. Chem. 2015, 80, 1365–1374. (g) Padhi, B.;
Reddy, D. S.; Mohapatra, D. K. Eur. J. Org. Chem. 2015, 3, 542–
a
conditions
(%)
o
1
2
.
.
(R)-Methyl-CBS,
THF, −20 C, 12 h
-
-
-
BH
3
.THF
o
L-Selectride
THF, −78 C, 1 h
-
o
3
4
.
.
NaBH
NaBH
4
4
MeOH, 0 C, 1 h
50/50
65/35
82
75
5
47. (h) Reddy, D. S.; Gaddam, J.; Devunuri, N.; Mohapatra, D. K.
o
Tetrahedron Lett. 2015, 56, 4299–4301. (i) Nagarjuna, B.;
Thirupathi, B.; Rao, C. V.; Mohapatra, D. K. Tetrahedron Lett.
2015, 56, 4916–4918.
, (L)-TarB-
MeOH, −78 C,
NO
2
12 h
1
1
0. Mohapatra, D. K.; Das, P. P.; Pattanayak, M. R.; Yadav, J. S. Chem.
Eur. J. 2010, 16, 2072–2078.
o
5
6
.
.
.
NaBH
NaBH
4
4
, CeCl
3
3
.7H
.7H
2
2
O
O
MeOH, −78 C, 1
72/28
76/24
-
88
87
-
1. (a) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J.
Am. Chem. Soc. 2000, 122, 8168–8179. (b) Dinh, M. T.; Bouzbouz,
S.; Peglion, J. L.; Cossy, J. Tetrahedron 2008, 64, 5703–5710.
2. Yu, W.; Mei, Y.; Jin, Z. Org. Lett. 2004, 6, 3217–3219.
3. (a) Bal, B. S.; Jr. Childers, W. E.; Pinnick, H. W. Tetrahedron 1981,
h
o
, CeCl
i-PrOH, −78 C, 1
1
1
h
o
7
(+)-DIP-Chloride
THF, 0 C-rt, 12 h
3
2
7, 2091–2096. (b) Mann, J.; Thomas, A. Tetrahedron Lett. 1986,
7, 3533–3534.
a
1
1
4. (a) Pearson, C.; Rinehart, K. L.; Sugano, M. Tetrahedron Lett. 1999,
0, 411–414. (b) Spaltenstein, A.; Leban, J. J.; Huang, J. J.;
Isolated yield after both MOM group deprotection.
4
In summary, an efficient and convergent diastereoselective
approach has been developed to synthesize isocladosporin and 3-
epi-isocladosporin in 10 longest linear sequence starting from
homoallylic alcohol 14 in 28% overall yield. Cross-metathesis,
isomerization followed by C-O and C-C bond formation
reactions to construct 2,6-trans-dihydropyran ring, base induced
isomerization, acylation of resulting benzyl lithium derivative
and Luche reduction of ketone 7.
Reinhardt, K. R.; Viveros, O. H.; Sigafoos, J.; Crouch, R.
Tetrahedron Lett. 1996, 37, 1343–1346.
5. (a) Chiarello, J.; Joullie, M. M. Tetrahedron 1988, 44, 41–48. (b)
Barret, A. G. M.; Morris, T. M.; Barton, D. H. R. J. Chem. Soc.
Perkin Trans. 1 1980, 2272.
6. Dodd, J. H.; Garigipati, R. S.; Weinreb, S. M. J. Org. Chem. 1982,
47, 4045–4049.
7. (a) Creger, P. L. J. Am. Chem. Soc. 1970, 92, 1396–1397. (b)
Barluenga, S.; Lopez, P.; Moulin, E.; Winssinger, N. Angew. Chem.
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Barluenga, S.; Totzke, F.; Winssinger, N. Chem. Eur. J. 2006, 12,
1
1
Acknowledgments
8
819–8834. (e) Fürstner, A.; Bindl, M.; Jean, L. Angew. Chem. Int.
Ed. 2007, 46, 9275–9278.
The authors thank CSIR, New Delhi for financial support as
part of XII Five Year plan programme under title ORIGIN (CSC-
1
8. (a) Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen, C. P.; Singh, V. K.
J. Am. Chem. Soc. 1987, 109, 7925–7926. (b) Corey, E. J.; Helal, C.
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Singh, V. K. Synthesis 1992, 605–617.
0108). S.M. and S.B. thank Council of Scientific and Industrial
Research (CSIR), New Delhi, India, for financial assistance in
the form of fellowships.
19. Surprisingly during reduction of keto group using (R)-Methyl-CBS
or L-Selectride, MOM-group was deprotected
.
Supporting Information
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi/xxxxxx.
References and notes
1
.
Blunt, J. W.; Copp, B. R.; Keyzers, R. A.; Munro, M. H. G.; Prinsep,
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2
.
2
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1
6
20
5
3
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A. Arch. Microbiol. 1978, 116, 253–257. (c) Podojil, M.; Sedmera,
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K.; Nemec, P. Folia Microbiol. (Prague) 1978, 23, 438–443. (d)
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H. G.; Crumley, F. G.; Farrist, G.; Cox, R. H.; Davis, E. E.; Thean, J.
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block, 0.32 x 0.20 x 0.12 mm , triclinic, space group P-1, a =
7.3291(6) Å, b = 7.5213(5) Å, c = 14.8356(10) Å, = 81.162(6)°,
3
3
.
=
78.711(6)°, = 66.488(5)°, V = 732.80(9) Å , Z = 2, T = 200(2) K,
–3
-1
2
0
max=50.00°, Dcalc (g cm ) = 1.325, F(000) = 312, (mm ) =
.098, 6216 reflections collected, 2516 unique reflections
int=0.1322), 1376 observed (I > 2 (I)) reflections, multi-scan
(
R
4
5
.
.
absorption correction, Tmin = 0.969, Tmax = 0.988, 667 refined
parameters, S = 0.961, R1 = 0.0811, wR2 = 0.2131 (all data R =
0
.1736, wR2 = 0.2838), maximum and minimum residual electron
-3
densities; Δmax = 0.43, Δmin= -0.34 (eÅ ).
2
2
2. (a) Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc.,
Madison, Wisconsin, USA. (b) Sheldrick, G. M. Acta Crystallogr.
2
008, A64, 112. (c) Farrugia, L. J. J. Appl. Cryst. 1997, 30, 565–565.
o 25
3. Spectral data of compound 1: Mp. 157–158 C; [α]
CHCl ); IR (KBr): υmax 3430, 2924, 2854, 1729, 1659, 1457, 1247,
164, 1092 cm ; H NMR (300 MHz, CD
D
−5.2 (c 0.55,
3
−1
1
1
3
OD): δ 7.88 (s, 1H), 6.19
(s, 1H), 6.18 (d, J = 2.1 Hz, 1H), 4.73 (m, 1H), 3.65 (m, 1H), 3.48
6
7
8
.
.
.
Zheng, H.; Zhao, C.; Fang, B.; Jing, P.; Yang, J.; Xie, X.; She, X. J.
Org. Chem. 2012, 77, 5656–5663.
Reddy, B. V. S.; Reddy, P. J.; Reddy, C. S. Tetrahedron Lett. 2013,
(
1
m, 1H), 2.92–2.80 (m, 2H), 1.89–1.72 (m, 3H), 1.63–1.54 (m, 3H),
.24–1.15 (m, 2H), 1.13 (d, J = 6.2 Hz, 3H); C NMR (75 MHz,
13
CD
3
OD) δ 171.5, 166.3, 165.6, 143.5, 107.9, 102.2, 101.6, 77.5,
5
4, 5185–5187.
7
5.2, 74.7, 42.9, 34.5, 34.4, 32.9, 24.7, 22.4; ESI-HRMS: m/z calcd.
(a) Tanaka, J.; Higa, T. Tetrahedron Lett. 1996, 37, 5535–5538. (b)
Smith, A. B.; Safonov, I. G.; Corbett, R. H. J. Am. Chem. Soc. 2002,
+
for C16
4. Spectral data of compound 2: Mp. 200–203 C; [α]
CHCl ); IR(KBr): υmax 3447, 2919, 2851, 1630, 1463, 1254, 1164,
H O [M + H] : 293.1383, found, 293.1380.
21 5
o 25
2
D
−41.0 (c 0.25,
1
24, 11102–11113. (c) Horton, P. A.; Koehn, F. E.; Longley, R. E.;
3
McConnell, O. J. J. Am. Chem. Soc. 1994, 116, 6015–6016. (d)
Hegde, V. R.; Puar, M. S.; Dai, P.; Patel, M.; Gullo, V. P.; Das, P.
−1
1
1
1
081 cm ; H NMR (300 MHz, CD
3
OD): δ 6.22 (s, 1H), 6.19 (s,
H), 4.71 (m, 1H), 3.59 (m, 1H), 3.47 (m, 1H), 2.97–2.86 (m, 2H),