Addition of Lithiated Methoxyallene to Aziridines
1077
tral Al2O3, h exan e–eth yl acetate 4:1) to yield 7d (69 m g, 69%) as a pale yellow viscous oil,
wh ich slowly crystallized at 4 °C, m .p. 88 °C. [α]D –32.5 (c 0.94, CHCl3). 1H NMR (CDCl3,
500 MHz): 2.30–2.32 (m , 1 H, 5-H), 2.33–2.36 (m , 1 H, 3-H), 2.39 (s, 3 H, ArMe), 2.51–2.60
(m , 2 H, 3-H, 5-H), 2.63–2.73 (m , 2 H, CH2Ph ), 3.39 (m c, 1 H, 6-H), 4.05 (m c, 1 H, 6-H), 4.64
(m c, 1 H, 2-H), 7.06–7.10, 7.19–7.28 (2 m , 2 H, 5 H, Ph , Ar), 7.53 (d, J = 8.5, 2 H, Ar). 13C NMR
(CDCl3, 125.8 MHz): 21.4 (q, ArMe), 38.7 (t, CH2Ph ), 40.47, 40.53 (2 t, C-3, C-6), 44.1 (t,
C-5), 56.1 (d, C-2), 126.8, 127.1, 128.6, 129.1, 129.8, 136.7, 136.8, 143.6 (5 d, 3 s, Ph , Ar),
206.5 (s, C-4). IR (KBr): 3080, 2970–2860 (=C–H, C–H), 1720 (C=O), 1340 (SO2N). For
C
19H21NO3S (343.5) calculated: 66.45% C, 6.16% H, 4.08% N; foun d: 66.31% C, 5.85% H,
3.78% N.
(1S,6R)-3-Tosyl-1,2,3,4,5,6-h exah ydro-2,6-m eth an o[3]ben zazocin e (9)
A solution of piperidon e 7d (558 m g, 1.62 m m ol) dissolved in eth an ol (10 m l) was cooled to
0 °C an d NaBH4 (184 m g, 4.88 m m ol) was added. Th e resultin g m ixture was stirred at room
tem perature for 18 h . Th e m ixture was quen ch ed with 2 M HCl an d th e m ixture was ex-
tracted with dieth yl eth er. Th e com bin ed organ ic ph ases were wash ed with saturated aque-
ous NaHCO3 solution , dried (an h ydrous Na2SO4), an d con cen trated in vacuo. Th e crude
product was filtered th rough a sh ort colum n (silica gel, pen tan e–eth yl acetate 1:1) to yield 8
(506 m g, 90%, two diastereom ers). Alcoh ol 8 (108 m g, 0.31 m m ol) was dissolved in toluen e
(20 m l), polyph osph oric acid (2 g) was added an d th e m ixture was stirred at room tem pera-
ture for 18 h . Th e m ixture was quen ch ed with saturated aqueous NaHCO3 solution . Th e
ph ases were separated an d th e aqueous ph ase was extracted with eth yl acetate. Th e com -
bin ed organ ic layers were wash ed with brin e, dried (an h ydrous MgSO4) an d con cen trated in
vacuo. Th e crude product was purified by colum n ch rom atograph y (silica gel, h exan e–eth yl
acetate 4:1, th en 1:1) to yield 9 (88 m g, 88%) as a colorless solid, m .p. 111–112 °C. [α]D –6.5
(c 0.15, CHCl3). 1H NMR (CDCl3, 500 MHz): 1.80 (m c, 2 H, 12-H), 1.90 (m c, 2 H, 13-H), 2.43
(s, 3 H, ArMe), 2.64 (d, J = 18.4, 1 H, 8-H), 2.75 (td, J = 3.1, 12.5, 1 H, 11-H), 2.98 (dd, J =
6.2, 18.4, 1 H, 8-H), 3.08 (m c, 1 H, 1-H), 3.63 (dd, J = 4.7, 12.5, 1 H, 11-H), 4.48 (m c, 1 H, 9-H),
7.06–7.11 (m , 4 H, Ar), 7.29, 7.71 (2 d, J = 8.0, 2 H each , Ar). 13C NMR (CDCl3, 125.8 MHz):
21.5 (q, ArMe), 30.6 (t, C-13), 31.8 (d, C-1), 32.1 (t, C-12), 33.2 (t, C-8), 38.0 (t, C-11), 47.6
(d, C-9), 126.1, 126.4, 127.0, 127.5, 128.9, 129.7, 135.6, 137.9, 138.8, 142.9 (6 d, 4 s, Ar).
IR (KBr): 3060–2850 (=C–H, C–H), 1335 (SO2N). For C19H12NO2S (327.1) calculated: 69.69% C,
6.46% H, 4.18% N; foun d: 69.62% C, 6.45% H, 4.19% N.
Meth yl (3S)-3-(4-Meth ylben zen e-1-sulfon am ido)butan oate (10b)
A solution of un purified allen e adduct 3b (200 m g, 0.71 m m ol) in dry m eth an ol (10 m l) was
cooled to –78 °C an d ozon e was bubbled in to th e solution un til a blue color persisted. Th en ,
th e excess of ozon e was purged out with oxygen . Rem ovin g th e solven t yielded th e crude
product, wh ich was recrystallized from a m ixture of h exan e–eth yl acetate to give 10b (153 m g,
78%) as a colorless solid, m .p. 77–78 °C. [α]D –23.7 (c 0.24, CHCl3); ref.24 m .p. 77–78 °C,
[α]D –22.4 (c 1.16, CHCl3). 1H NMR (CDCl3, 500 MHz): 1.14 (d, J = 6.7, 3 H, 4-H), 2.43 (s, 3 H,
ArMe), 2.44 (m c, 2 H, 2-H), 3.62 (s, 3 H, OMe), 3.68 (m c, 1 H, 3-H), 5.26 (d, J = 8.4, 1 H,
NH), 7.30, 7.76 (2 d, J = 8.1, 2 H each , Ar). 13C NMR (CDCl3, 125.8 MHz): 21.0, 21.4 (2 q,
C-4, ArMe), 40.6 (t, C-2), 46.5 (d, C-3), 51.7 (q, OMe), 127.0, 129.7, 137.9, 143.3 (2 d, 2 s,
Ar), 171.6 (s, CO).
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1069–1080