Cyclopropanation of 5-Aryl-1-diazo-1-mesitylsulfonyl-5-hexen-2-ones
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under investigation, the findings of the substituent effect References and Notes
made in this study inform us that the enantioselectivity
[1] H. Nozaki, H. Takaya, S. Moriuti, R. Noyori, Tetrahe-
in the cyclopropanation of the styrene type substrates
could be changed by the protective group for the hy-
droxy group on the phenyl group. The chiral building
blocks prepared through this study are now being con-
verted to natural products, and the related synthetic
studies will be reported in due course.
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Experimental Section
(1R,5R)-2-Oxo-5-phenyl-1-(2,4,6-
trimethylphenylsulfonyl)bicyclo[3.1.0]hexane (14)
[CuOTf]2 ·C6H6 (1.2 mg, 0.00238 mmol, 10 mol % as CuOTf)
was placed in a dried flask (10 mL) under an argon atmosphere
and to this flask was added a solution of ligand 1e (1.9 mg,
0.00714 mmol, 15 mol %) in toluene (0.5 mLꢀ2) via a cannula.
The mixture was stirred at room temperature for 0.5 h and then
to the light blue solution was added a solution of 13 (18.2 mg,
0.0476 mmol) in toluene (0.5 mLꢀ2) via a cannula. The reac-
tion mixture was stirred at room temperature for 2.5 h,
quenched with NH4OH aqueous solution (2 mL), extracted
with ether (5 mL) and CH2Cl2 (5 mLꢀ2). The combined or-
ganic layer was washed with brine (10 mL), dried over
Na2SO4, and evaporated. The residue was purified by prepara-
tive TLC (benzene/ethyl acetate¼10/1) to afford 14 as a white
solid; yield: 16.0 mg (96% ee, 95%). The absolute configuration
was determined by X-ray crystallographic analysis of the re-
crystallized 14. The ee was determined by HPLC [(254 nm,
Daicel Chiral Cell AS-H 0.46 cm fꢀ25 cm; hexane/2-prop-
anol¼3/1; flow rate¼0.5 mL/min); retention time: 18.0 min
for ent-14, 25.0 min for 14; Rf ¼0.48 (hexane/ethyl acetate¼
2/1)]; mp 162–1638C (hexane/CH2Cl2); [a]D19: À181 (c 0.45,
CHCl3, 100% ee); IR (KBr): n¼2984, 1728, 1604, 1450, 1316,
1300, 1266, 1204, 1146, 1058, 1034, 764, 698, 668, 608,
´
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dron: Asymmetry 1999, 10, 1903–1911; h) S. G. Kim,
C. W. Cho, K. H. Ahn, Tetrahedron 1999, 55, 10079–
10086; for a-diazo esters, see: i) P. Mueller, Y. F. Allen-
bach, S. Grass, Tetrahedron: Asymmetry 2005, 16,
2007–2013; j) M. P. Doyle, W. Hu, T. M. Weathers Jr.,
Chirality 2003, 15, 369–373; k) B. Saha; T. Uchida; T.
Katsuki Tetrahedron: Asymmetry 2003, 14, 823–836;
l) S. Iwasa, S. Tsushima, K. Nishiyama, Y. Tsuchiya, F.
Takezawa, H. Nishiyama, Tetrahedron: Asymmetry
2003, 14, 855–865; m) C.-M. Che, J.-S. Huang, F.-W.
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son, J. P. Vitale, S. A. Stanley, J. Am Chem. Soc. 2000,
122, 5718–5728; a-diazophosphonate, see: p) J. D.
Moore, P. R. Hanson, Tetrahedron: Asymmetry 2003,
14, 873–880.
516 cmÀ1
;
1H NMR (400 MHz, CDCl3): d¼7.63 (d, J¼
7.8 Hz, 2H), 7.42 (dd, J¼7.1, 7.8 Hz, 2H), 7.35 (t, J¼7.1 Hz,
1H), 6.94 (s, 2H), 3.05 (d, 5.4 Hz, 1H), 2.65 (s, 6H), 2.70–2.20
(m, 4H), 2.08 (d, J¼5.4 Hz, 1H); 13C-NMR (100 MHz,
CDCl3): d¼203.9, 142.9, 140.6, 136.4, 135.2, 132.0, 129.7,
128.3, 59.4, 48.2, 34.1, 30.5, 26.8, 23.5, 21.1; HR-MS (FAB):
m/z¼355.1339; calcd. for C21H22O3SHþ: 355.1368.
[4] a) M. Honma, T. Sawada, Y. Fujisawa, M. Utsugi, H. Wa-
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Acknowledgements
This workwas financially supported in part by the Uehara Me-
morial Foundation, a Waseda University Grant for Special Re-
search Projects, and a Grant-in-Aid for Scientific Research on
Priority Areas “Creation of Biologically Functional Molecules”
(No. 17035082) from the Ministry of Education, Science, Sports,
Culture and Technology, Japan. We are also indebted to 21COE
“Practical Nano-Chemistry.”
Adv. Synth. Catal. 2005, 347, 1527 – 1532
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
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