(s, CH); dH (400 MHz, D2O) 1.31 (m, 2H, CH2), 1.50 (m, 2H, CH2),
1.82 (m, 2H, CH2), 2.10 (m, 2H, CH2), 3.13 (m, 2H, NHCH2), 3.31
(m, 6H, NHCH2), 3.41 (m, 2H, NHCH); dC (100 MHz, CD3OD)
24.3 (2 × CH2), 29.7 (2 × CH2), 39.7 (2 × NHCH2), 43.2 (2 ×
NHCH2), 57.7 (2 × NHCH).
added and the reaction mixture was stirred for 72 h. The resulting
mixture was filtered through alumina using ethyl acetate as the elu-
ant. Evaporation of the solvent and recrystallisation from diethyl
ether–hexane at −20 C afforded 1-[(4-methylphenyl)sulfonyl]-2-
◦
phenylaziridine 25 as an ◦off-white solid (40 mg, 0.15 mmol, 49%)
mp 86–88 ◦C (lit.17 88–90 C). Found: MH+ 274.0903. C15H15NO2S
requires:MH+ 274.0902. mmax (KBr, cm−1) 3359 (w, NHTs), 3042
(m, NH), 2977 (w, CH), 1316 (s, SO2NH), 1154 (s, SO2NH); dH
(400 MHz, CDCl3) 2.43 (d, J 4.5 Hz, 1H, CHH), 2,47 (s, 3H,
C6H4CH3), 3.02 (d, J 7.2, 1H, CHH), 3.82 (dd, J 7.2, 4.5, 1H,
CHPh), 7.25–7.38 (m, 7H, ArCH), 7.91 (d, J 8.3, 2H, C6H4); dC
(100 MHz, CDCl3) 21.9 (C6H4CH3) 36.1 (CH2), 41.3 (CH), 126.8
(2 × ArCH), 128.2 (2 × ArCH), 128.5 (ArC), 128.8 (ArCH), 130.0
(2 × ArCH), 135.3 (ArC), 144.8 (ArC). Chiral HPLC indicated
that the two enatiomeric products were formed in a 1 : 1 ratio; tR =
11.45 min and 13.98 min
(7aR,11aR)-1,4,7-Trimethyldodecahydro-1H -1,4,7-benzotri-
azonine 1. (7aR,11aR)-Dodecahydro-1H-1,4,7-benzotriazonine
trihydrochloride (R,R)-20 (305 mg, 1.04 mmol) was dissolved in
water (20 cm3) and the solution was made basic (pH 14) by the
addition of solid NaOH (ca. 250 mg). The basic solution was
extracted with dichloromethane (×4, 10 cm3) and the combined
organic phases were dried (Na2SO4), filtered and evaporated to
give a pale yellow oil. To this oil was added formaldehyde (38%,
0.8 cm3) and formic acid (90%, 0.9 cm3) and the solution was
heated to reflux (bath temp. 90 ◦C) under a nitrogen atmosphere for
20 h. After cooling to room temperature the reaction was acidified
(pH 1) with conc. HCl (1 cm3) and the volatiles were removed
under reduced pressure. The aqueous solution was extracted with
dichloromethane (×2, 10 cm3). The aqueous phase was made basic
(pH 14) by addition of solid NaOH (ca. 250 mg). The basic
solution was extracted with dichloromethane (×4, 10 cm3), and
the combined organic phases were dried (Na2SO4), filtered and
evaporated to give a pale yellow oil (185 mg, 0.82 mmol, 79%).
Found: MH+ 226.2280. Calculated for C13H27N3 MH+: 226.2283;
[a]D −48.8 (c = 0.5, CHCl3). mmax (liq. film, cm−1) 2933 (m, CH),
2857 (m, CH), 2791 (m, CH), 1666 (s), 1451 (s, CH), 732 (s, CH2);
dH (400 MHz, CDCl3) 1.05 (m, 4H, CH2), 1.63 (m, 2H, CH2), 1.73
(m, 2H, CH2), 2.29 (s, 9H, NCH3), 2.48 (m, 6H, NCH2), 2.60 (m,
2H, NCH2) 2.95 (m, 2H, NCH); dC (100 MHz, CDCl3) 25.2 (2×
CH2), 27.0 (2× CH2), 40.2 (2 × NCH3), 46.8 (NCH3), 54.4 (2×
NCH2), 54.8 (2× NCH2), 63.6 (2 × NCH).
Acknowledgements
This work was funded under the Adventurous Chemistry award
EP/C532309/1 which funded R. T. We also thank the EPSRC for
a studentship (to G. S.). We are also grateful (K. R.-D.) for funding
from the ERASMUS association and the region Rhoˆne-Alpes. We
also thank Raghu R. Morthala for recording a number of spectra.
References
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Copper(II) complex formation
To a solution of copper(II) chloride (162 mg, 1.2 mmol) in
anhydrous acetonitrile (20 cm3) under a nitrogen atmosphere was
added a solution of (7aR,11aR)-1,4,7-trimethyldodecahydro-1H-
1,4,7-benzotriazonine 1 (271 mg, 1.2 mmol) in acetonitrile (5 cm3).
The resulting green solution was stirred under nitrogen for 90 min,
whereupon, it was diluted with acetonitrile (50 cm3), and a solution
of silver trifluoroacetate (530 mg, 2.4 mmol) in acetonitrile (10 cm3)
was added. The now bright blue solution was stirred for 1 h
giving a precipitate of silver(II) chloride. The reaction mixture
was filtered through Celite and the solvent was evaporated to
afford a blue solid. Recystallisation from acetone–diethyl ether
gave the title compound as blue rhomboid crystals (328 mg,
0.64 mmol, 53%) that were suitable for X-ray crystallography. Mp
211 ◦C (decomp.) Found: C, 39.4; H, 5.3; N, 8.1%. Calculated for
C17H27CuF6N3O4: C, 39.6; H, 5.3; N, 8.2%. mmax (KBr, cm−1) 2943
(m, CH), 2859 (w, CH), 1705 (s), 1690 (s), 1422 (s), 1204 (s), 1180
(s), 1126 (s), 723 (s); kmax [CH3CN, nm (e)] 284 (4806), 548 (28),
652 (88).
Aziridination of styrene 24
A mixture of [N-(4-tolylsulfonyl)imino]phenyliodinane42 (112 mg,
0.3 mmol) and complex 22 (8 mg, 15 lmol, 5 mol%) in acetonitrile
(2 cm3) under a nitrogen atmosphere was stirred for 2 h until a
homogeneous solution resulted. Styrene (0.35 cm3, 3 mmol) was
13 K. P. McCue and J. R. Morrow, Inorg. Chem., 1999, 38, 6136–6142;
E. L. Hegg, K. A. Deal, L. Kiessling and J. Burstyn, Inorg. Chem., 1997,
36, 1715–1718; A. O’Donoghue, S. Y. Pyun, M.-Y. Yang, J. R. Morrow
and J. P. Richard, J. Am. Chem. Soc., 2006, 128, 1615–1621.
This journal is
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