L. F. Silva Jr., S. A. Quintiliano / Tetrahedron Letters 50 (2009) 2256–2260
2259
OH
O
H
O
5
mol % I2, PhCHO,
CH Cl2, rt, 2.5 h
0%
2
Ph
Ph
+
7
1
9
20
(2:1)
21
5
mol % I2,
-MeOC CHO
CH Cl2, rt, 24 h
OH
Ar
4
6 4
H
O
H
O
H
O
2
-
H
+
8
1%
H
H
H
H
2
5
Ar
Ar
HO
HO
5:1)
22
(
+)-23
(+)-24
(
Scheme 6.
Me
NTs
Ph
δ+
δ+
H
NHTs 20 mol % I
CHO
Cl2, rt, 72 h
0%
trans:cis = 5:1)
2
-H
C
2
6
H
5
Ph
H
CH
N E-28
Ts
trans-27
cis-27
6
(
26
Me
δ+
NTs
Ph
H
-
H
+
H
δ
N
Z-28
Ts
Ph
Scheme 7.
compounds and homoallylic alcohols, which were used in equimo-
lar amounts. Furthermore, the aza-Prins version occurs under anal-
ogous conditions. Thus, an expeditious entry toward new
hexahydrobenzo[f]-chromenes and hexahydrobenzo[f]isoquino-
line has been disclosed. Additional studies for these Prins and
aza-Prins cyclizations are being developed in our group.
47, 3242; (d) Bahnck, K. B.; Rychnovsky, S. D. J. Am. Chem. Soc. 2008, 130, 13177;
e) Kopecky, D. J.; Rychnovsky, S. D. J. Am. Chem. Soc. 2001, 123, 8420; (f) Van
Orden, L. J.; Patterson, B. D.; Rychnovsky, S. D. J. Org. Chem. 2007, 72, 5784; (g)
Overman, L. E.; Pennington, L. D. J. Org. Chem. 2003, 68, 7143.
(
5. (a) Jasti, R.; Rychnovsky, S. D. J. Am. Chem. Soc. 2006, 128, 13640; (b) Hiebel, M.;
Pelotier, B.; Piva, O. Tetrahedron 2007, 63, 7874; (c) Cheung, L. L.; Marumoto, S.;
Anderson, C. D.; Rychnovsky, S. D. Org. Lett. 2008, 10, 3101; (d) Tadpetch, K.;
Rychnovsky, S. D. Org. Lett. 2008, 10, 4839; (e) Miranda, P. O.; Carballo, R. M.;
Martín, V. S.; Padrón, J. I. Org. Lett. 2009, 11, 357.
6
.
Few examples were reported using ketones: (a) Yadav, J. S.; Reddy, B. V. S.;
Krishna, V. H.; Swamy, T.; Kumar, G. G. K. S. Can. J. Chem. 2007, 85, 412. and
references therein; (b) Miles, R. B.; Davis, C. E.; Coates, R. M. J. Org. Chem. 2006,
71, 1493.
For recent reviews concerning iodine, see: (a) Stavber, S.; Jereb, M.; Zupan, M.
Synthesis 2008, 1487; (b) Togo, H.; Iida, S. Synlett 2006, 2159; (c) Smith, M. B. e-
EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, Ltd,
Acknowledgments
The authors wish to thank to FAPESP and CNPq for continuous
financial support. Professor H. M. C. Ferraz is acknowledged for
fruitful discussion in the fragmentation reactions.
7
.
2001; (d) French, A. N.; Bissmire, S.; Wirth, T. Chem. Soc. Rev. 2004, 33, 354; (e)
Das, S.; Borah, R.; Devi, R. R.; Thakur, A. J. Synlett 2008, 2741; For some
reactions using iodine as Lewis acid, see: (f) Sun, J.; Dong, Y.; Cao, L.; Wang, X.;
Wang, S.; Hu, Y. J. Org. Chem. 2004, 69, 8932; (g) Bosco, J. W. J.; Agrahari, A.;
Saikia, A. K. Tetrahedron Lett. 2006, 47, 4065.
Yadav, J. S.; Reddy, B. V. S.; Kumar, G. G. K. S. N.; Swamy, T. Tetrahedron Lett.
2007, 48, 2205.
Supplementary data
Spectroscopic data and experimental procedures are available.
8.
9. For selected recent examples, see: (a) Kishi, Y.; Nagura, H.; Inagi, S.; Fushigami,
T. Chem. Commun. 2008, 3876; (b) Armstrong, A.; Bhonoah, Y.; Shanahan, S. J.
Am. Chem. Soc. 2007, 72, 8019; (c) Carballo, R. M.; Ramírez, M. A.; Rodríguez, M.
L.; Martín, V. S.; Padrón, J. I. Org. Lett. 2006, 8, 3837; (d) Cesati, R. R., III;
Katzenellenbogen, J. Org. Lett. 2000, 2, 3635; (e) Yadav, J. S.; Reddy, B. V. S.;
Chaya, D. N.; Kumar, G. G. K. S. N.; Aravind, S.; Kunwar, A. C.; Madavi, C.
Tetrahedron Lett. 2008, 49, 3330.
10. (a) Silva, L. F., Jr.; Quintiliano, S. A. P.; Craveiro, M. V.; Vieira, F. Y. M.; Ferraz, H.
M. C. Synthesis 2007, 355; (b) Silva, L. F., Jr.; Quintiliano, S. A. P.; Ferraz, H. M. C.;
Santos, L. S.; Eberlin, M. N. J. Braz. Chem. Soc. 2006, 17, 981; (c) Ferraz, H. M. C.;
Silva, L. F., Jr. Tetrahedron 2001, 57, 9939; (d) Silva, L. F.; Craveiro, M. V.
Molecules 2005, 10, 1419.
11. For examples of 5-endo-trig iodocyclization, see: (a) Barks, J. M.; Weingarten, G.
G.; Knight, D. W. J. Chem. Soc., Perkin Trans. 1 2000, 3469; (b) Bedford, S. B.; Bell,
K. E.; Bennett, F.; Hayes, C. J.; Knight, D. W.; Shaw, D. E. J. Chem. Soc., Perkin
Trans. 1 1999, 2143; (c) Barks, J. M.; Knight, D. W.; Seaman, C. J.; Weingarten, G.
G. Tetrahedron Lett. 1994, 35, 7259; (d) Knight, D. W. Prog. Heterocycl. Chem.
2002, 14, 19; Terminal olefins and endocyclic olefins afforded 4-exo-tet
iodocyclization products: (e) Galatsis, P.; Parks, D. J. Tetrahedron Lett. 1994, 35,
6611.
References and notes
1
.
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For reviews regarding Prins reaction and Prins cyclization, see: (a) Pastor, I. M.;
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S. M. Quim. Nova 2006, 29, 834; (c) Clarke, P. A.; Santos, S. Eur. J. Org. Chem.
(
2
4
2
.
.
2
3
2
006, 2045; (d) Adams, D. R.; Bhatnagar, S. P. Synthesis 1977, 661; (e) Arundale,
E.; Mikeska, L. A. Chem. Rev. 1952, 51, 505.
4
.
For examples, see: (a) Vintonyak, V. V.; Kunze, B.; Sasse, F.; Maier, M. E. Chem.
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Preite, M. D.; Cuellar, M. A. Chem. Commun. 2004, 1970; (c) Kocovsk y´ , P.;
2
008, 10, 1637; (c) Woo, S. K.; Kwon, M. S.; Lee, E. Angew. Chem., Int. Ed. 2008,