COMMUNICATIONS
in yields of between 50 and 55% regardless of the position of
the halogen substituent.
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J. Am. Chem. Soc. 1997, 119, 10857.
A comparison of the new domino hydroamination aryne
cyclization reaction with known cyclizations of 2-(2-chloro-
[
11]
phenyl)ethylamines
clearly shows the superiority of
the new method. The yields of the indoline products ob-
tained are superior to the reported values by about a factor
of 3.
KOtBu-catalyzed hydroaminations of aromatic olefins with
anilines make pharmacologically interesting N-(2-arylethyl)-
anilines accessible with 100% atom economy and in a
particularly viable manner in good to excellent yields. The
excellent chemo- and regioselectivities are an important
advantage over classical syntheses of N-substituted anilines.
The use of 2- or 3-substituted halostyrenes as starting
materials has enabled the synthesis of N-substituted indolines
by a novel domino reaction. Very recent experiments indicate
that this reaction is not limited to anilines, but that aliphatic
[
5] Selected reviews on domino reactions: L. F. Tietze, U. Beifuû, Angew.
Chem. 1993, 105, 137; Angew. Chem. Int. Ed. Engl. 1993, 32, 131;
b) L. F. Tietze, Chem. Rev. 1996, 96, 115.
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Caignard, B. Guardiola (ADIR et Cie., France), EP-B 527687 A2,
1
992 [Chem. Abstr. 1993, 118, 254750e]; b) Z. Budai, P. Benko, L.
Pallos (Egyesult Gyogyszer, Hungary), HU-B 155783 [Chem. Abstr.
969, 71, 21854n]; c) J. G. Berger, W. K. Chang, J. A. Kozlowski, G.
1
Zhou (Schering Corp., USA), US-A 5530125 A, 1992 [Chem. Abstr.
1994, 120, 134315m].
[
12]
amines also undergo analogous reactions.
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b) P. G. Williard, G. J. MacEwan, J. Am. Chem. Soc. 1989, 111,
7
4
671; c) F. M. Mackenzie, R. E. Mulvey, J. Am. Chem. Soc. 1996, 118,
721.
[
8] a) B. Robinson, The Fischer Indole Synthesis, Wiley-Interscience, New
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Synth. 1994, 1, 145; d) R. J. Sundberg, Indoles, Academic Press, San
Diego, 1996.
Experimental Section
Synthesis of N-phenyl-2,3-dihydroindole (9): In an Ace pressure tube
38 mL) 2-chlorostyrene (0.28 g, 2.0 mmol) and aniline (0.28 g, 3.0 mmol)
(
were dissolved in toluene (10 mL) under argon. After addition of
potassium tert-butylalcoholate (0.67 g, 6.0 mmol), the sealed reaction
vessel was placed in an oil bath preheated to 1358C and the reaction
mixture was stirred vigorously. After 36 h the mixture was allowed to cool
to room temperature and water (20 mL) was added with stirring. The
aqueous phase was extracted three times with dichloromethane (10 mL).
Subsequently the combined organic phases were dried over magnesium
sulfate, and the solvent was removed under vacuum. The resulting crude
product was separated by column chromatography with hexane as eluent.
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b) J. F. Hartwig, S. Richards, D. Bara nÄ ano, F. Paul, J. Am. Chem. Soc.
1996, 118, 3626; c) M. S. Driver, J. F. Hartwig, J. Am. Chem. Soc. 1996,
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Buchwald, J. Am. Chem. Soc. 1998, 120, 9722.
1
Compound 9 was obtained in 53% (0.21 g) yield. H NMR (360 MHz,
3
2
58C, CDCl
3
): d 7.32 (dd, J(H,H) 8.0, 7.1 Hz, 2H, m-Ph-H), 7.21 (d,
3
3
J(H,H) 8.0 Hz, 2H, o-Ph-H), 7.14 (d, J(H,H) 7.1 Hz, 1H, Ar), 7.12 (d,
3
3
3
J(H,H) 8.0 Hz, 1H, Ar), 7.05 (dd, J(H,H) 8.0, 7.5 Hz, 1H, Ar), 6.94 (t,
3
J(H,H) 7.1 Hz, 1H, p-Ph-H), 6.73 (dd, J(H,H) 7.5, 7.1 Hz, 1H, Ar),
3
3
[10] a) K. Aoki, A. J. Peat, S. L. Buchwald, J. Am. Chem. Soc. 1998,
120, 3068; b) M. Beller, C. Breindl, T. H. Riermeier, unpublished
results.
3
.92 (t, J(H,H) 8.4 Hz, 2H, NCH
2
), 3.10 (t, J(H,H) 8.4 Hz, 2H, CH
2
);
1
3
1
C{ H} NMR (90 MHz, 258C, CDCl
3
): d 147.1 (quart. Ph), 144.2 (quart.
Ar-C-N), 131.2 (quart. Ar-C), 129.1 (m-Ph), 127.1 (Ar), 125.0 (Ar), 120.9
(
Ar), 118.8 (Ar), 117.7 (o-Ph), 108.2 (p-Ph), 52.1 (NCH
2
), 28.2 (CH
2
); MS
[11] a) R. Huisgen, H. König, Chem. Ber. 1959, 92, 203; b) R. Huisgen, H.
König, N. Bleeker, Chem. Ber. 1959, 92, 424; c) H. König, R. Huisgen,
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Soc. Perkin 1 1975, 2502.
(
70 eV): m/z (%): 195 (5) [M ], 165 (70), 116, 91 (100), 77.
Received: May 12, 1998 [Z11845IE]
[12] M. Beller, C. Breindl, unpublished results.
German version: Angew. Chem. 1998, 110, 3571 ± 3573
Keywords: aminations ´ arynes ´ cyclizations ´ domino
reactions ´ potassium
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2] E. Mutschler, Arzneimittelwirkungen, 7th ed., Wissenschaftliche
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Angew. Chem. Int. Ed. 1998, 37, No. 24
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