Communications
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b) quinoline A, when treated with 1a and NaBr in MeCN at
808C, leads to an intractable mixture of products and consumes
all the starting material; quinoline B does not react with 1a
under the same conditions, thus both materials are returned
untouched; no cyclopropanantion was observed in these
reactions.
Scheme 6. Catalytic elaboration of [4.1.0]-bicycloalkenes in complex
molecule synthesis. Cp=cyclopentadienyl, TMS=trimethylsilyl.
ing the application of this new catalytic reaction in the
synthesis of architecturally complexnatural products.
Experimental Section
The cinchona alkaloid catalyst (20 mol%) was added to a mixture of
the chloroketone 1 (1.0 equiv), sodium bromide (0.25 equiv), and
sodium carbonate (1.3 equiv) in anhydrous acetonitrile (0.1m), and
the reaction mixture was stirred at 808C for 24–36 h until complete, as
shown by TLC and LC–mass-spectrometric analysis. The reaction was
concentrated and diluted with diethyl ether before filtering through a
pad of silica. After concentration of the filtrate the residue was
purified by flash column chromatography on silica gel to afford the
[4.1.0]-bicycloalkane.
[10] 1’-deazo cinchona alkaloids have been synthesized previously
through a nontrivial route: a) C. Exner, A. Pfaltz, M. Studer, H.-
U. Blaser, Adv. Synth. Catal. 2003, 345, 1253; b) E. V. Dehmlow,
S. Düttmann, B. Neumann, H.-G. Stammler, Eur. J. Org. Chem.
2002, 2087.
[11] We also tested catalysts containing C2’-Ph (83% yield, 96% ee),
iPr (59% yield, 98% ee), and tBu (46% yield, 93% ee), but the
Me-MQ/ Me-MQD catalysts gave the best results.
Received: May 28, 2006
Published online: August 4, 2006
Keywords: asymmetric synthesis · cinchona alkaloids ·
.
cyclopropanation · intramolecular reactions · organocatalysis
[12] See the Supporting Information for details.
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ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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