PAPER
Asymmetric Halonium Additions to Isolated Alkenes
1897
soln was heated at 40 °C for 1 h. The mixture was then cooled to
0 °C and bubbled with CO2 for 5 min. The reaction was quenched
with 1 M aq HCl (10 mL) and the mixture was extracted with
EtOAc (3 × 10 mL). The organic layers were combined, dried
(MgSO4), filtered, and concentrated. The residue was purified by
column chromatography [silica gel, hexanes–EtOAc (4:1 to 0:1)] to
afford 1,2,3,4-tetrahydronaphthalene-1-carboxylic acid as a light-
yellow crystalline solid; yield: 0.22 g (37%).
HPLC: AD-H column, 1.0 mL/min, hexane–i-PrOH (9:1), 30 °C,
240 nm; tR (major) = 10.09 min, tR (minor) = 13.61 min (3% ee).
Acknowledgment
We thank the NSF (CHE-0619638) for an X-ray diffractometer and
Professor Gerard Parkin, Dr. Aaron Sattler, and Mr. Serge Ruccolo
for crystallographic analysis of compounds 12 and 20a. Financial
support was provided by Columbia University, the NSF (CAREER
Award CHE-0844593 and Predoctoral Fellowships to A.P.B. and
D.S.T.), Ludwig-Maximilians-University-Munich (study stipend to
S.A.L.), the ACS Petroleum Research Fund (47481-G), the Camille
and Henry Dreyfus Foundation (New Faculty Award to S.A.S.), and
generous gifts from Bristol-Myers Squibb, Eli Lilly, and Amgen.
A portion of the newly synthesized carboxylic acid (0.145 g, 0.754
mmol, 1.0 equiv) was dissolved in MeOH (5.0 mL) at 25 °C and
treated by addition of a 2.0 M soln of TMSCHN2 in hexanes (2.26
mL, 4.52 mmol, 6.0 equiv) over 20 min. The mixture was stirred for
an additional 5 min at 25 °C and then the reaction was quenched by
dropwise addition of AcOH (0.2 mL). The mixture was concentrat-
ed directly to afford the desired crude methyl ester as a colorless vis-
cous solid; yield: 0.161 g (99%).
Supporting Information for this article is available online at
The crude methyl ester (0.75 mmol assumed) was dissolved in
CH2Cl2 (3.0 mL) and the soln was treated with Et3N (0.523 mL,
3.75 mmol, 5.0 equiv). The resulting soln was cooled to –20 °C and
MsCl (0.116 mL, 1.50 mmol, 2.0 equiv) was added dropwise over
5 min. The mixture was then warmed slowly to 25 °C over 1 h. DBU
(0.561 mL, 3.75 mmol, 5.0 equiv) was added and the soln was
stirred at 25 °C for a further 1 h. The reaction was then quenched
with H2O (20 mL) and the mixture was extracted with 1:1 hexanes–
EtOAc (3 × 20 mL). The organic layers were combined, washed
with 1 M aq HCl (2 × 5 mL) and sat. aq NaHCO3 (5 mL), dried
(MgSO4), filtered, and concentrated. The residue was purified by
column chromatography [silica gel, hexanes–EtOAc (1:0 to 9:1)] to
give methyl 5,6-dihydronaphthalene-1-carboxylate as a colorless
viscous oil; yield: 0.026 g (18%).
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References
(1) For recent reviews, see: (a) Chen, G.; Ma, S. Angew. Chem.
Int. Ed. 2010, 49, 8306. (b) Castellanos, A.; Fletcher, S. P.
Chem. Eur. J. 2011, 17, 5766. (c) Snyder, S. A.; Treitler, D.
S.; Brucks, A. P. Aldrichimica Acta 2011, 44, 27.
(d) Hennecke, U. Chem. Asian J. 2012, 7, 456. (e) Snyder, S.
A.; Brucks, A. P. In Asymmetric Synthesis II: More Methods
and Applications; Christmann, M.; Bräse, S., Eds.; Wiley–
VCH: Weinheim, 2012, Chap. 20. (f) Denmark, S. E.;
Kuester, W. E.; Burk, M. T. Angew. Chem. Int. Ed. 2012, 51,
10938.
Finally, the methyl ester (0.026 g, 0.14 mmol, 1.0 equiv) was dis-
solved in THF (2.0 mL) and H2O (1.0 mL), and the soln was cooled
to 0 °C. Solid LiOH (0.034 g, 1.4 mmol, 10 equiv) was added and
the mixture was stirred vigorously at 25 °C for 2 d. The mixture was
then cooled to 0 °C and the reaction was quenched with 1 M aq HCl
(5 mL). The mixture was extracted with EtOAc (3 × 10 mL), and the
organic layers were combined, dried (MgSO4), filtered, and concen-
trated. The residue was purified by column chromatography [silica
gel, hexanes–EtOAc (1:1)] to give acid 46 as a white crystalline sol-
id; yield: 0.023 g (90%); Rf = 0.24 (silica gel, hexanes–EtOAc, 2:1).
(2) (a) Juliá, S.; Ginebreda, A. Tetrahedron Lett. 1979, 23,
2171. (b) Tanaka, Y.; Sakuraba, H.; Nakanishi, H. J. Chem.
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2009, 131, 5744. (g) Nicolaou, K. C.; Simmons, N. L.; Ying,
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8134. For examples of asymmetric seleniranium and
thiiranium ions see: (h) Denmark, S. E.; Voler, T. Chem.
Eur. J. 2009, 15, 11737. (i) Denmark, S. E.; Kalyani, D.;
Collins, W. R. J. Am. Chem. Soc. 2010, 132, 15752.
(j) Denmark, S. E.; Kornfilt, D. J. P.; Vogler, T. J. Am.
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T. Org. Lett. 2012, 14, 256.
IR (film): 2954 (br), 1680, 1456, 1274, 932, 752 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.87 (d, J = 8.0 Hz, 1 H), 7.50 (d,
J = 10.0 Hz, 1 H), 7.31 (d, J = 7.2 Hz, 1 H), 7.18 (t, J = 7.6 Hz, 1
H), 6.26 (dt, J = 9.6, 4.4 Hz, 1 H), 2.83 (t, J = 8.0 Hz, 2 H), 2.34–
2.27 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 172.9, 137.2, 135.3, 132.3, 131.7,
129.5, 126.2, 125.4, 125.0, 28.3, 22.3.
HRMS (EI): m/z [M]+ calcd for C11H10O2: 174.0681; found:
174.0680.
(3) For pioneering work on bromonium transfer, see:
(a) Bellucci, G.; Bianchini, R.; Chiappe, C.; Marioni, F.;
Ambrosetti, R.; Brown, R. S.; Slebocka-Tilk, H. J. Am.
Chem. Soc. 1989, 111, 2640. (b) Bennet, A. J.; Brown, R. S.;
McClung, R. E. D.; Klobukowski, M.; Aarts, G. H. M.;
Santarsiero, B. D.; Bellucci, G.; Bianchini, R. J. Am. Chem.
Soc. 1991, 113, 8532. (c) Brown, R. S.; Nagorski, R. W.;
Bennet, A. J.; McClung, R. E. D.; Aarts, G. H. M.;
Klobukowski, M.; McDonald, R.; Santarsiero, B. D. J. Am.
Chem. Soc. 1994, 116, 2448. For additional critical studies,
see: (d) Rodebaugh, R.; Fraser-Reid, B. Tetrahedron 1996,
52, 7663. (e) Chiappe, C.; De Rubertis, A.; Jaber, A.; Lenoir,
D.; Wattenbach, C.; Pomelli, C. S. J. Org. Chem. 2002, 67,
7066. (f) Denmark, S. E.; Burk, M. T.; Hoover, A. J. J. Am.
Chem. Soc. 2010, 132, 1232.
trans-1-Acetyl-8-iodo-6,7,8,8a-tetrahydrobenzo[cd]indol-
2(1H)-one (48)
Prepared by the procedure used to synthesize 14.
White crystalline solid; yield: 7 mg (70%); Rf = 0.31 (silica gel,
hexanes–EtOAc, 3:1).
IR (film): 2934, 2854, 1734, 1716, 1253, 750 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.68 (d, J = 7.2 Hz, 1 H), 7.49 (t,
J = 7.6 Hz, 1 H), 7.44 (d, J = 7.6 Hz, 1 H), 5.49 (d, J = 8.8 Hz, 1 H),
3.91 (td, J = 9.2, 5.2 Hz, 1 H), 3.08 (m, 1 H), 2.88 (m, 1 H), 2.76 (m,
1 H), 2.70 (s, 3 H), 4.56 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 172.8, 168.3, 142.6, 135.2, 132.7,
130.1, 127.8, 122.7, 62.5, 36.7, 27.5, 26.2, 22.8.
HRMS (FAB): m/z [M + H]+ calcd for C13H13NIO2: 341.9991;
found: 341.9987.
(4) (a) Snyder, S. A.; Treitler, D. S. Angew. Chem. Int. Ed. 2009,
48, 7899. (b) Snyder, S. A.; Treitler, D. S.; Brucks, A. P.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 1886–1898