C O M M U N I C A T I O N S
References
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Figure 1. ORTEP drawings of the spiro-quinolines 7a and 7b.
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and a terminal acetylene, was cyclized under the previously
described conditions to give the olefin migration product 9 in
moderate yield (53%) but good enantioselectivity (86% ee) (eq 4).
(10) (a) Takemoto, T.; Sodeoka, M.; Sasai, H.; Shibasaki, M. J. Am. Chem.
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J. Org. Chem. 1995, 60, 4322-4323. (c) Kojima, A.; Takemoto, T.;
Sodeoka, M.; Shibasaki, M. J. Org. Chem. 1996, 61, 4876-4877. (d)
Ohshima, T.; Kagechika, K.; Adachi, M.; Sodeoka, M.; Shibasaki, M. J.
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(11) So far, the N-Ts protecting group is essential. Other N-protecting groups
instead of N-Ts do not tolerate the reaction conditions.
(12) Hegedus, L. S. Transition Metals in the Synthesis of Complex Organic
Molecules; University Science Books: Mill Valley, CA, 1999.
(13) Double bond migrations of cyclic olefin are also observed in the
asymmetric Mizoroki-Heck reaction. (a) Ozawa, F.; Kubo, A.; Matsu-
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(14) Crystal data for 7a in X-ray analysis: formula C23H23NO5S, triclinic, space
group P-1 (No. 2), a ) 8.7188(5) Å, b ) 14.5607(7) Å, c ) 8.5946(5)
Å, R ) 99.563(3)°, â ) 89.5260(1)°, γ ) 73.718(4)°, V ) 1031.05(10)
Å3, Z ) 2, and D ) 1.371 g cm-3. X-ray diffraction data were collected
on a Rigaku R-AXIS CS diffractometer with graphite-monochromated
Mo KR (λ ) 0.71069 Å) at - 40 °C, and the structure was solved by
direct methods (SIR97). The final cycle of full-matrix least-squares
refinement was based on 4233 observed reflections (I > 3σ(I)) and 271
variable parameters and converged to R ) 0.0647 and Rw ) 0.1817.
Crystallographic data (excluding structure factors) for the structure reported
in this paper have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-196469. Copies of
the data can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail:
deposit@ccdc.cam.ac.uk).
(15) Crystal data for 7b in X-ray analysis: formula C21H21NO3S, monoclinic,
space group P21/c (No. 14), a ) 9.3996(2) Å, b ) 19.4020(4) Å, c )
9.8885(2) Å, â ) 92.8800(1)°, V ) 1801.10(6) Å3, Z ) 4, and D ) 1.355
g cm-3. X-ray diffraction data were collected on a Rigaku R-AXIS CS
diffractometer with graphite-monochromated Mo KR (λ ) 0.71069 Å) at
-40 °C, and the structure was solved by direct methods (SIR97). The
final cycle of full-matrix least-squares refinement was based on 4115
observed reflections (I > 3σ(I)) and 235 variable parameters and converged
to R ) 0.0508 and Rw ) 0.1391. Crystallographic data have been deposited
as no. CCDC-196470.
In conclusion, we have developed a highly enantioselective
method for the synthesis of quinoline via ene-type cyclization of
1,7-enynes catalyzed by the cationic BINAP-palladium(II) com-
plex. This is the first example of asymmetric ene-type cyclization
affording six-membered ring compounds, with a quaternary carbon
center or a spiro-ring.
Acknowledgment. This work is dedicated to Professor Frederick
E. Ziegler of Yale University on the occasion of his 65th birthday
on March 29, 2003.
Supporting Information Available: Typical experimental proce-
dures and spectral data for 1-9 and crystallographic data collection
parameters for spiro-ring products (4a, 7a, 7b) (PDF and CIF). This
org.
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