Communications
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The applicability of the newtechnology to other synthetic
problems is currently under study and will constitute the
subject of future reports.
Received: March 31, 2004 [Z460178]
[15] Only one stereoisomer of the product was apparent within the
1
limits of H- (300 MHz) and 13C NMR (75 MHz) spectrometry.
Keywords: antitumor agents · cyclization · spiro compounds ·
sulfonamides · total synthesis
.
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[17] For related processes, see reference [3g].
[18] For a discussion, see: R. V. Stevens, Acc. Chem. Res. 1984, 17,
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[19] The 1H NMR spectra of (ꢀ)-4 synthesized herein ([a]2D5 = ꢀ398;
c = 0.5 in CH2Cl2), could be superimposed on those of (ꢁ )-2-
epicylindricine C published by Weinreb and co-workers[3e] (see
Supporting Information).
[3] Total synthesis of (ꢀ)-cylindricine C: a) G. A. Molander, M.
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cylindricines C, D, and E: b) B. M. Trost, M. T. Rudd, Org. Lett.
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[21] The 1H NMR spectra of (ꢀ)-3 synthesized herein could be
superimposed on those of (ꢀ)-cylindricine C reported by
Molander and Roenn[3a] (see Supporting Information), and the
specific rotations were also essentially identical: [a]2D5 = ꢀ668
(c = 0.5 in CH2Cl2) for 3 versus [a]2D5 = ꢀ648 (c = 0.2 in CH2Cl2)
for reference [3a].
[4] For synthetic studies on the structurally related alkaloids,
fasicularin and lepadiformine, see: a) H. Abe, S. Aoyagi, C.
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[5] Unpublished results from these laboratories; details will be
provided in a forthcoming full paper.
[6] The absolute configuration of cylindricine C is unknown.[2] We
chose to prepare (ꢀ)-4 from d-homotyrosine for comparison
purposes because at the beginning of our investigations the only
enantioselective synthesis of (ꢀ)-4 reported in the literature was
that by Molander and Roenn.[3a]
[7] a) SOCl2/MeOH; b) MsCl/TEA (excess), CH2Cl2, 08C, (forma-
tion of the N,O-dimesyl derivative), 91% over two steps;
c) NaBH4/EtOH/THF, 94%; d) NaOH/dioxane, 808C, 90%.
Ms = methanesulfonyl, TEA = triethylamine.
[8] Under identical conditions, cyclization of the corresponding
methyl ether proceeded with d.r. = 3.5:1 and that of the TBDMS
ether with d.r. = 4.5:1.
[9] The structure of this material was confirmed by an X-ray
crystallographic study of its desilylated analogue. The selectivity
of the 1,4-addition of PhSH to 8 appears to be due to a Felkin–
Anh-type stereoelectronic effect created by the strongly electro-
negative sulfonamide nitrogen atom. For examples, see: a) E. L.
Eliel, S. H. Wilen, Stereochemistry of Organic Compounds,
Wiley, NewYork, 1994, p. 875; b) S. Bennabi, K. Narkunan, L.
Rousset, D. Bouchu, M. A. Ciufolini, Tetrahedron Lett. 2000, 41,
8873, and references therein.
[10] R. Mozingo, D. E. Wolf, S. A. Harris, K. Folkers, J. Am. Chem.
Soc. 1943, 65, 1013.
[11] Weaker bases were ineffective for deprotonation of 10, in accord
with: L. A. Paquette, S. C. Ra, J. D. Schloss, S. M. Leit, J. C.
Gallucci, J. Org. Chem. 2001, 66, 3564.
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Angew. Chem. Int. Ed. 2004, 43, 4336 –4338