G. F. Keaney, J. L. Wood / Tetrahedron Letters 46 (2005) 4031–4034
4033
Moran, M.; Nageli, I. J. Phys. Org. Chem. 1996, 9, 341–
47; (c) Padwa, A.; Flick, A. C.; Leverett, C. A.; Stengel,
T. J. Org. Chem. 2004, 69, 6377–6386.
film/NaCl) 3106 (m), 2871 (w), 1728 (w), 1607 (m), 1531
(s), 1349 (s), 1311 (m), 1167 (s), 1092 (m) cm ; HRMS
À1
3
(FAB) m/z found: 382.9701 [calcÕd for C H BrN O S
1
4
12
2
4
4
. (a) Nishikori, H.; Katsuki, T. Tetrahedron Lett. 1996, 37,
9
(M+H): 382.9701].
N-p-Nitrobenzenesulfonyl-1,2-(dihydronathalenyl)-aziridine
245–9248; (b) Noda, K.; Hosoya, N.; Irie, R.; Ito, Y.;
Katsuki, T. Synlett 1993, 469–471; (c) Mahy, J. P.;
Battioni, P.; Mansuy, D. J. Am. Chem. Soc. 1986, 108,
1
(Entry 4). Cream-colored foam. H NMR (500 MHz,
CDCl ) d 8.35 (d, J = 8.8 Hz, 2H), 8.13 (d, J = 9.2 Hz,
3
1
Tetrahedron Lett. 1992, 33, 1001–1004.
. Au, S. M.; Fung, W. H.; Cheng, M. C.; Che, C. M.; Peng,
S. M. Chem. Commun. 1997, 11, 1655–1656.
. (a) White, R. D.; Keaney, G. F.; Slown, C. D.; Wood, J.
L. Org. Lett. 2004, 6, 1123–1126; (b) White, R. D.; Wood,
J. L. Org. Lett. 2001, 3, 1825–1827; (c) Sudau, A.; Munch,
W.; Bats, J. W.; Nubbemeyer, U. Chem. Eur. J. 2001, 7,
079–1080; (d) OÕConnor, K. J.; Wey, S. J.; Burrows, C. J.
2H), 7.31 (d, J = 7.6 Hz, 1H), 7.27–7.23 (m, 1H), 7.18 (t,
J = 7.6 Hz, 1H), 7.07 (d, J = 7.4 Hz, 1H), 3.93 (d,
J = 7.0 Hz, 1H), 3.72 (br d, J = 7.0 Hz, 1H), 2.79–2.68
(m, 1H), 2.59 (dd, J = 5.4, 15.8 Hz, 1H), 2.34–2.28 (m,
5
1
3
6
1H), 1.75 (tdd, J = 1.7, 5.5, 14.7 Hz, 1H) ppm; C NMR
(125 MHz, CDCl ) d 150.6, 144.7, 136.6, 129.6, 129.2,
3
129.0, 128.9, 128.9, 128.6, 126.7, 124.4, 124.4, 43.4, 42.9,
24.7, 20.1 ppm; IR (thin film/NaCl) 3106 (m), 3039 (w),
2940 (m), 2855 (w), 1731 (w), 1607 (m), 1531 (s), 1400 (m),
6
11–621; (d) Tian, X. R.; Hudlicky, T.; Konigsberger, K.
À1
J. Am. Chem. Soc. 1995, 117, 3643–3644; (e) Overman, L.
E.; Tomasi, A. L. J. Am. Chem. Soc. 1998, 120, 4039–4040.
. Guthikonda, K.; Du Bois, J. J. Am. Chem. Soc. 2002, 124,
1349 (s), 1333 (s), 1162 (s), 1090 (m) cm ; HRMS (FAB)
m/z found: 331.0752 [calcÕd for C H N O S (M+H):
1
6
15
2
4
7
8
331.0752].
N-p-Nitrobenzenesulfonyl-9-azabicyclo[6.1.0]nonane (Entry
1
. (a) Brown, D. S.; Elliott, M. C.; Moody, C. J.; Mowlem,
3672–13673.
1
5). Cream-colored solid, m.p. 143–144 °C. H NMR
T. J.; Marino, J. P.; Padwa, A. J. Org. Chem. 1994, 59,
2
(500 MHz, CDCl ) d 8.38 (d, J = 8.7 Hz, 2H), 8.14 (d,
3
447–2455; (b) Brodsky, B. H.; Du Bois, J. Org. Lett.
004, 6, 2619–2621.
. For examples of previous applications of Rh (pfm) , see:
J = 8.9 Hz, 2H), 2.94–2.87 (m, 2H), 2.07–1.98 (m, 2H),
1.67–1.22 (comp m, 10H) ppm; C NMR (125 MHz,
1
3
2
9
CDCl ) d 150.6, 145.0, 129.0, 124.4, 45.1, 26.4, 26.3,
2
4
3
(
a) Ref. 8a; (b) Moody, C. J.; Miah, S.; Slawin, A. M. Z.;
Mansfield, D. J.; Richards, I. C. Tetrahedron 1998, 54,
689–9700; (c) Savinov, S. N.; Austin, D. J. Chem.
Commun. 1999, 11, 1813–1814.
0. All other catalysts (Cu(OTf), Cu(OTf)
Rh (OAc) , Rh (OTFA) , and Rh (pfb) ) screened for
25.3 ppm; IR (thin film/NaCl) 3105 (m), 3070 (w), 2924 (s),
2858 (m), 1530 (s), 1351 (s), 1304 (s), 1295 (s), 1159 (s)
cm ; HRMS (FAB) m/z found: 311.1065 [calcÕd for
À1
9
C H N O S (M+H): 311.1065].
trans-N-Trichloroethoxysulfonyl-2-methyl-3-propylaziridine
1
4
19
2
4
1
1
2
,
Rh
2
(oct)
4
,
1
(Entry 6). Clear oil. H NMR (500 MHz, CDCl
2
4
2
4
2
4
3
) d 4.78 (s,
this reaction led to no appreciable aziridine formation.
1. Rh (pfm) Catalyst Preparation: Rhodium acetate (25 mg,
2H), 2.79–2.69 (comp m, 2H), 1.77–1.41 (comp m, 4H),
1.53 (d, J = 5.8 Hz, 3H), 0.96 (t, J = 7.0 Hz, 3H) ppm;
1
3
C
2
4
0
0
1
.056 mmol, 1.0 equiv), perfluorobutyramide (120 mg,
.56 mmol, 10.0 equiv), and Na CO (60 mg, 0.56 mmol,
0.0 equiv) were dissolved in 3.0 mL of chlorobenzene in a
NMR (125 MHz, CDCl ) d 93.3, 79.5, 50.8, 46.0, 32.0,
3
2
3
20.2, 14.7, 13.7 ppm; IR (thin film/NaCl) 2962 (m), 2935
(m), 2876 (w), 1450 (w), 1366 (s), 1250 (w), 1181 (s), 1166
À1
microwave vial. The reaction was conducted under
microwave irradiation (Biotage Initiator, 205 W) for
(m) cm ; HRMS (FAB) m/z found: 309.9839 [calcÕd for
8 3 3
C H15Cl NO S (M+H): 309.9838].
3
0 min at250 °C. The purple reaction mixture was cooled
cis-N-Trichloroethoxysulfonyl-2-methyl-3-propylaziridine
1
to room temperature and extracted with FC-72 (perfluoro-
n-hexane, Acros) three times. The fluorous extracts were
concentrated under reduced pressure. Excess perfluorobu-
tyramide was removed by sublimation. The complex could
be used without further purification, or purified by silica
gel chromatography (9:1–3:1 hexanes/ethyl acetate) to give
(Entry 7). Clear oil. H NMR (500 MHz, CDCl ) d 4.79
3
(d, J = 10.5 Hz, 1H), 4.76 (d, J = 10.8 Hz, 1H), 3.03–2.96
(m, 1H), 2.91–2.85 (m, 1H), 1.60–1.45 (comp m, 4H), 1.31
1
3
(d, J = 6.1 Hz, 3H), 0.99 (t, J = 7.1 Hz, 3H) ppm;
C
NMR (125 MHz, CDCl ) d 93.2, 79.4, 47.0, 42.5, 28.3,
3
20.4, 13.8, 12.0 ppm; IR (thin film/NaCl) 2962 (m), 2876
(w), 1466 (w), 1450 (w), 1379 (s), 1367 (s), 1254 (w), 1181
1
9
Rh
(
2 4
(pfm) (31 mg, 53% yield) as a blue solid. F NMR
À1
376 MHz, CD CN, C H CF standard at À63.7 ppm)
(s) cm ; HRMS (FAB) m/z found: 309.9839 [calcÕd for
3
6
5
3
À82.0, À117.8, À127.9 ppm.
C H Cl NO S (M+H): 309.9838].
N-Trichloroethoxysulfonyl-2,2,3-trimethylaziridine (Entry
8
15
3
3
1
2. Representative Aziridination Procedure: To a solution of
Cl
7
2
1
3
CCH
2
SO
3
NH
(126 mg, 0.55 mmol, 1.1 equiv) in
.0 mL of C H was added olefin substrate (0.50 mmol,
3
8). Clear oil. H NMR (400 MHz, CDCl ) d 4.76 (d,
1
1
J = 10.8 Hz, 1H), 4.71 (d, J = 10.8 Hz, 1H), 2.97 (q,
J = 5.9 Hz, 1H), 1.62 (s, 3H), 1.32 (s, 3H), 1.29 (d,
6
6
.0 equiv), MgO (46 mg, 1.15 mmol, 2.3 equiv), and
(pfm) (5.3 mg, 0.005 mmol, 0.01 equiv). The blue
(209 mg,
.65 mmol, 1.3 equiv) was added. The reaction was run at
1
3
Rh
2
4
3
J = 5.9 Hz, 3H) ppm; C NMR (100 MHz, CDCl ) d
mixture was cooled to 5 °C and PhI(OAc)
2
93.3, 79.3, 51.7, 50.1, 20.9, 20.4, 13.0 ppm; IR (thin film/
NaCl) 3000 (m), 2972 (s), 2936 (m), 1626 (w), 1462 (s),
0
5
À1
°C for approximately 2 h, and then at room temperature
1415 (m), 1366 (s), 1253 (m), 1181 (s), 1090 (s) cm
;
for 8 h. The reaction was filtered through a Celite plug,
washed repeatedly with CH Cl , and the combined
filtrates were concentrated under reduced pressure. The
material was purified by silica gel chromatography to
provide the aziridine product.
HRMS (FAB) m/z found: 295.9681 [calcÕd for
C H Cl NO S (M+H): 295.9681].
N-p-Nitrobenzenesulfonyl-2,2,3-trimethylaziridine (Entry
2
2
7
13
3
3
1
8). White solid, m.p. 114–116 °C. H NMR (500 MHz,
3
CDCl ) d 8.36 (d, J = 8.8 Hz, 2H), 8.11 (d, J = 8.8 Hz,
1
3. N-p-Nitrobenzenesulfonyl-2-(2-bromophenyl)-aziridine (Entry
2
2H), 3.06 (q, J = 6.1 Hz, 1H), 1.76 (s, 3H), 1.33 (s, 3H),
1.17 (d, J = 6.0 Hz, 3H) ppm; C NMR (125 MHz,
CDCl ) d 150.3, 147.3, 128.4, 128.4, 124.3, 124.3, 53.6,
3
1
13
). Cream-colored solid, m.p. 131–132 °C. H NMR
(
J = 8.6 Hz, 2H), 7.41 (d, J = 7.8 Hz, 1H), 7.15–6.98 (comp
400 MHz, CDCl
3
) d 8.29 (d, J = 8.6 Hz, 2H), 8.11 (d,
49.3, 21.9, 20.9, 13.0 ppm; IR (thin film/NaCl) 3116 (m),
3000 (w), 2968 (w), 2931 (w), 2867 (w), 1607 (m), 1531 (s),
1460 (w), 1380 (m), 1351 (s), 1319 (s), 1300 (s), 1162 (s)
m, 3H), 4.03 (dd, J = 4.7, 7.4 Hz, 1H), 3.04 (d, J = 7.2 Hz,
1
3
1
H), 2.29 (d, J = 4.7 Hz, 1H) ppm; C NMR (100 MHz,
CDCl ) d 150.9, 143.7, 134.0, 132.7, 130.1, 129.5, 129.5,
27.9, 127.5, 124.5, 124.5, 123.5, 42.1, 36.5 ppm; IR (thin
À1
3
cm ; HRMS (FAB) m/z found: 271.0753 [calcÕd for
1
C H N O S (M+H): 271.0752].
1
1
15
2
4