1
104
C. Camarero et al.
LETTER
MeO
MeO
MeO
(5) Brewster, A. G.; Broady, S.; Hughes, M.; Moloney, M. G.;
Woods, G. Org. Biomol. Chem. 2004, 2, 1800; and
references therein.
i, ii
2a
+
N
N
MeO
O
O
Me
Me
Me
(6) (a) Manteca, I.; Sotomayor, N.; Lete, E. Tetrahedron Lett.
1
996, 33, 7841. (b) Collado, M. I.; Sotomayor, N.; Villa,
M.-J.; Lete, E. Tetrahedron Lett. 1996, 37, 6193.
c) Collado, M. I.; Manteca, I.; Sotomayor, N.; Villa, M. J.;
Me
2
CO Bn
R3
R3
2
CO Bn
(
(
1SR,2RS,10bSR)-8
(1SR,2SR,10bSR)-8'
Lete, E. J. Org. Chem. 1997, 62, 2080. (d) Manteca, I.;
Etxarri, B.; Ardeo, A.; Arrasate, S.; Osante, I.; Sotomayor,
N.; Lete, E. Tetrahedron 1998, 54, 12361.
R3 = Me, 57%, dr =
R3 = allyl, 50%, dr =
8
a, 86
:
:
8a', 14
8b', 20
8b, 80
(
7) For reviews on Parham cyclization, see: (a) Parham, W. E.;
Bradsher, C. K. Acc. Chem. Res. 1982, 15, 300. (b) Gray,
M.; Tinkl, M.; Snieckus, V.In Comprehensive
Scheme 6 Reagents and conditions: (i) Me CuLi, THF, –78 °C to
2
3
0
°C, 16 h; (ii) R I, r.t., 24 h, NH Cl–NH OH.
4 4
Organometallic Chemistry II, Vol. 11; Abel, E. W.; Stone, F.
G. A.; Wilkinson, G., Eds.; Pergamon: Exeter, 1995, 66–92.
(c) Ardeo, A.; Collado, M. I.; Osante, I.; Ruiz, J.;
Sotomayor, N.; Lete, E. In Targets in Heterocyclic Systems,
Vol. 5; Atanassi, O.; Spinelli, D., Eds.; Italian Society of
Chemistry: Rome, 2001, 393–418. (d) Mealy, M. M.;
Bailey, W. F. J. Organomet. Chem. 2002, 649, 59.
In conclusion, conjugate addition reactions of nucleo-
philes to the g-lactam unit of dihydropyrrolo[2,1-a]iso-
quinolones allowed the stereocontrolled formation of
carbon–carbon bonds at the C-1 position. The attack of the
nucleophile occurred parallel to the angular substituent,
except when this substituent or the nucleophile were
bulky.
(
(
e) Sotomayor, N.; Lete, E. Curr. Org. Chem. 2003, 7, 275.
f) Arrasate, S.; Sotomayor, N.; Lete, E. In New Methods for
the Asymmetric Synthesis of Nitrogen Heterocycles; Vicario,
J. L.; Badía, D.; Carrillo, L., Eds.; Research Signpost: India,
Acknowledgment
2005, 223–248.
(
8) For examples of the tandem Parham cyclization–a-amido-
Financial support from MCYT (BQU2003-03239), and Universi-
dad del País Vasco/Euskal Herriko Unibertsitatea is gratefully ack-
nowledged. We also thank UPV/EHU for grants (I.G., C.C.).
alkylation reaction, see: (a) González-Temprano, I.;
Sotomayor, N.; Lete, E. Synlett 2002, 593. (b) González, I.;
Osante, I.; Sotomayor, N.; Lete, E. J. Org. Chem. 2004, 69,
3875. (c) Osante, I.; Lete, E.; Sotomayor, N. Tetrahedron
References and Notes
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9) For reviews on N-acyliminium ion cyclizations, see:
(
(
1) (a) Perlmutter, P. Conjugate Addition Reactions in Organic
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Comprehensive Asymmetric Catalysis I–III, Vol. 3;
(
4
a) Speckamp, W. N.; Hiemstra, H. Tetrahedron 1985, 41,
367. (b) Hiemstra, H.; Speckamp, W. N. In The Alkaloids,
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c) Hiemstra, H.; Speckamp, W. N. In Comprehensive
(
Organic Synthesis, Vol. 2; Trost, B. M.; Fleming, I., Eds.;
Pergamon Press: Oxford, 1991, 1047–1082. (d) de Koning,
H.; Speckamp, W. N. Stereoselective Synthesis, In Houben-
Weyl, Methoden der organischen Chemie, Vol. E21b;
Helmchen, G.; Hoffmann, R. W.; Muzler, J.; Schaumann, E.,
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W. N.; Moolenaar, M. J. Tetrahedron 2000, 56, 3817.
Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H., Eds.; Springer:
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ARKIVOC 2002, (vii), 167. (f) Iguchi, M.; Yamada, K.;
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In Topics in Organometallic Chemistry, Vol. 5; Hodgson, D.
M., Ed.; Springer: Berlin, 2003, 21–36. (g) Davies, S. G.;
Smith, A. D.; Price, P. D. Tetrahedron: Asymmetry 2005, 16,
(
f) Marson, C. M. ARKIVOC 2001, (i), 1. (g) Maryanoff, B.
E.; Zhang, H.-C.; Cohen, J. H.; Turchi, I. J.; Maryanoff, C.
A. Chem. Rev. 2004, 104, 1431. (h) Royer, J.; Bonin, M.;
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2833. (h) Wu, G.; Huang, M. Chem. Rev. 2006, 106, 2596.
(
2) See, for example: (a) Tamaru, Y.; Harada, T.; Iwawoto, H.;
Yoshida, Z.-I. J. Am. Chem. Soc. 1978, 100, 5221.
(
b) Mpango, G. B.; Mahalanabis, K. K.; Damghani, Z. M.;
Snieckus, V. Tetrahedron Lett. 1980, 21, 4823.
c) Mpango, G. B.; Snieckus, V. Tetrahedron Lett. 1980, 21,
827. (d) Hashimoto, M.; Hashimoto, K.; Shirahama, H.
(
10) Etxarri, B.; González-Temprano, I.; Manteca, I.; Sootmayor,
N.; Lete, E. Synlett 1999, 1486.
(
4
(
11) Conjugate addition reaction of enolates and cuprates to the
unactivated dihydropyrroloisoquinolones always failed, and
unreacted starting material was always recovered: González-
Temprano, I. PhD Thesis; Universidad del País Vasco:
Spain, 2003.
Tetrahedron 1996, 52, 1931. (e) Forns, P.; Díez, A.;
Rubiralta, M. Tetrahedron 1996, 52, 3563. (f) Forns, P.;
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(
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a) Seebach, D. Synthesis 1969, 17. (b) Krief, A.
Tetrahedron 1980, 36, 2531. (c) Page, P. C. B.; van Niel, M.
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Chem. Soc. 1978, 100, 5221. (b) Tamaru, Y.; Harada, T.;
Yoshida, Z. J. Am. Chem. Soc. 1979, 101, 1316.
4
(
(
12) See reference 6c.
(
(
13) See for instance: Osante, I.; Abdullah, M. N.; Arrasate, S.;
Sotomayor, N.; Lete, E. ARKIVOC 2007, (iv), 206.
14) Typical Procedure: MeLi (1.50 mL of a 1.6 M solution, 2.4
mmol) was added dropwise over a suspension of CuI (228
mg, 1.2 mmol) in anhyd THF (5 mL) at 0 °C. After 30 min,
the mixture was cooled to –78 ºC, and a solution of lactam
(
(
2a (157 mg, 0.4 mmol) in THF (10 mL) was added. The
reaction mixture was stirred for 3 h, allowed to warm to 0 ºC,
and stirred at this temperature for 12 h. The reaction was
(c) Gómez-Pardo, D.; Desmaele, D.; d’Angelo, J.
Tetrahedron Lett. 1992, 33, 6632.
Synlett 2007, No. 7, 1101–1105 © Thieme Stuttgart · New York