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A. Akhatou et al. / Tetrahedron 63 (2007) 6232–6240
(d¼7.77 ppm) in 13C NMR spectra. Data reported as
follows: s¼singlet, d¼doublet, t¼triplet, q¼quartet, m¼
multiplet, br s¼broad singlet; integration; coupling con-
stant(s) in hertz. Enantiomeric excesses (ee’s) of sulfoxides
(75 MHz, CDCl3): d 134.6, 130.3, 129.7, 129.2, 129.9,
128.6, 128.5, 128.2, 128.1, 128.1, 128.0, 127.7, 127.5,
127.3, 126.9, 126.8, 126.3, 125.9, 125.7, 124.7, 80.3 (Ar-
CH(O)N), 56.26 (Ar-CH2N); [a]2D0 +601 (c 0.5, CH2Cl2).
1
were determined by H NMR (400 MHz) using (R)-(ꢀ)-
(3,5-dinitrobenzoyl)-a-phenylethylamide17 as a chiral shift
reagent versus racemic compounds resulting from peracidic
(m-CPBA) oxidation. Optical rotations were measured on
a polarimeter with a sodium lamp and are reported as fol-
5.2.3. (S)-4,15-Diphenyl-2,3-dihydro-1H-dinaphtho[2,1-
c;10,20-e]azepine 5. (S)-3,30-Diphenyl-3,5-dihydro-1H-(3-
propenyl)dinaphth[2,1-c;10,20-e]azepine. To a degassed
acetonitrile solution (25 mL) of (S)-(ꢀ)-2,20-bis(bromo-
methyl)-1,10-binaphthyl 4 (5.56 g, 12.6 mmol, 1 equiv)
was added (2.9 mL, 3 equiv) of allylamine at room temper-
ature and under argon. The reaction mixture was heated at
55 ꢁC for 5 h but remained heterogeneous. The reaction mix-
ture was brought to room temperature, poured into a satu-
rated solution of sodium hydrogen carbonate. After
extraction with dichloromethane, the collected organic
phases were dried over magnesium sulfate, filtered, and con-
centrated. The resulting oil was purified by flash chromato-
graphy (gradient CH2Cl2–CH2Cl2/MeOH 30:1) to yield
4.9 g of a white solid (96%).
ꢁT
lows: ½aꢂD (c g/100 mL, solvent). The mass spectrum was
performed at 70 eV, mass range 35–400. Azepine 3 and
dibromide 4 were synthetized following a known procedure.16
5.2. Synthesis of oxaziridine (S)-1
5.2.1. (S)-1H-Dinaphtho[2,1-c:10,20-e]azepine 6. Small
portions of an aqueous solution of NaOCl at 15 ꢁC were
added to a solution of amine (S)-3 (450 mg, 1.52 mmol) in
dichloromethane (6 mL) until disappearance of the starting
amine and the quantitative formation of chloramine. The
organic phase was treated at 0 ꢁC under stirring, with 1 M
sodium hydroxide in methanol until disappearance of chlor-
amine. The aqueous phase was extracted with dichloro-
methane and the organic phases were combined and dried
with magnesium sulfate. Removal of the solvent left an
oil, which was purified by chromatography (silica gel,
dichloromethane) to give 394 mg of pure imine (S)-6 (white
foam). Yield 89%.
Rf (CH2Cl2): 0.25; MS (ESI positive): 487.2 [M+], calculated
487.6; H NMR (200 MHz, CDCl3):d 7.99–7.95 (m, 4H,
1
Ar-H), 7.66–7.63 (d, 4H, 6.18 Hz, Ar-H), 7.51–7.26 (m,
12H, Ar-H), 5.58–5.47 (m, 1H, CH]CH2), 4.76–4.71 (d,
1H, 10.2 Hz, cis-CH]CH2), 4.61–4.52 (d, 1H, 17.18 Hz,
trans-CH]CH2), 4.02–3.96 (d, 2H, 12.36 Hz, Ar-CH2),
3.12–3.05 (d, 2H, 12.62 Hz, Ar-CH2), 2.76–2.45 (m, 2H,
NCH2C]C); 13C NMR (75 MHz, CDCl3): d 142.3, 141.3,
137.3, 136.8, 133.5, 132.6, 131.6, 131.0, 130.2, 129.2,
129.0, 128.5, 127.9, 126.7, 126.5, 116.8, 56.07, 51.03.
Rf (CH2Cl2/NH4OH): 0.4; mp 144.5–146 ꢁC; [a]D20 +238.5 (c
1
10, CH2Cl2); IR (neat) 1613.2 cmꢀ1 (n C]N); H NMR
(200 MHz, CDCl3): d 8.58–8.57 (d, 1H, J1¼2.15 Hz,
Ar-CH]N), 8.02–7.1 (m, 12H, Ar-H), 5.01–4.95 (d, 1H,
J2¼10.74 Hz, Ar-CH2N), 3.98–3.91 (dd, 1H, J1¼2.15 Hz,
J2¼10.74 Hz, Ar-CH2N); 13C NMR (75 MHz, CDCl3):
d 162.4 (C]N), 141.0, 136.9, 133.1, 132.9, 132.3, 131.7,
129.2, 128.9, 128.5, 128.2, 128.0, 127.1, 126.3, 126.0,
125.8, 125.3, 124.3, 56.0 (Ar-CH2N). Anal. Calcd for
C22H15N: C, 90.07; H, 5.15; N, 4.77. Found: C, 89.43; H,
5.27; N, 4.75.
Under nitrogen atmosphere, a degassed dichloromethane
solution (30 mL) of -(S)-3,30-diphenyl-3,5-dihydro-1H-(3-
propenyl)-dinaphth[2,1-c;10,20-e]azepine (3 g, 6.15 mmol,
1 equiv), N,N-dimethylbarbituric acid (2.88 g, 18.46 mmol,
3 equiv), Pd(OAc)2 (83 mg, 0.123 mmol, 2 mol %), and
PPh3 (141 mg, 0.54 mmol, 4.3 equiv/Pd(OAc)2) was stirred
overnight at 35 ꢁC. The reaction mixture was poured into
a saturated hydrogen carbonate solution and extracted three
times with dichloromethane. The collected organic phases
were dried with magnesium sulfate, filtered, and concen-
trated in vacuo to yield a brown oil, which was purified on
silica gel using (CH2Cl2/MeOH from 50:1 to 20:1) as an
eluent and gave a white foam (74%).
5.2.2. (S)-1H-1,2-Oxydo-dinaphtho[2,1-c:10,20-e]azepine
1. m-Chloroperbenzoic acid (230 mg, 1.5 mmol, 1.1 equiv
of active oxygen) was added in small portions at 0 ꢁC to a
solution of imine 6 (364 mg, 1.24 mmol, 1 equiv) in 3 mL
of dichloromethane and 15 mL of methanol. After comple-
tion of the addition, sodium hydrogen carbonate (104 mg,
1 equiv) was added and the reaction was left until complete
disappearance of the imine. The reaction mixture was
diluted with dichloromethane, washed with a saturated solu-
tion of sodium thiosulfate, sodium hydrogen carbonate, and
finally with brine. The collected organic phases were dried
with magnesium sulfate, filtered, and concentrated. The
resulting yellow foam was purified by flash chromatography
(dichloromethane) to give pure oxaziridine (S)-1 as an amor-
phous solid (307 mg, 80%).
[a]2D0 +248.4 (c 0.5, CHCl3); MS (ESI positive): 447.2
[M] C34H25N, calculated 447.54; 1H NMR (300 MHz,
CDCl3): d 7.97–7.95 (m, 4H), 7.63–7.60 (m, 4H), 7.51–
7.40 (m, 8H), 7.33–7.27 (m, 4H), 4.06–4.02 (d, 2H,
12.63 Hz), 3.42–3.38 (d, 2H, 12.6 Hz); 13C NMR (75 MHz,
CDCl3): d 141.17, 139.81, 136.07, 132.57, 130.83, 129.72,
128.30, 128.22, 127.52, 127.21, 125.91, 125.79, 44.35
(C2, C20).
5.2.4. (S)-4,15-Diphenyl-1H-dinaphtho[2,1-c:10,20-e]aze-
pine 7. Small portions of aqueous NaOCl were added at
15 ꢁC to a solution of amine (S)-5 (600 mg, 1.34 mmol) in
dichloromethane (8 mL) until disappearance of the starting
reagent and the quantitative formation of chloramine. The
phases were separated, and the organic phase was added
dropwise at 0 ꢁC under stirring to a sodium hydroxide
solution in methanol (NaOH¼1 g; MeOH¼18 mL). The
Rf (CH2Cl2): 0.65; mp: 132–134 ꢁC. MS (ESI positive):
ꢃ
309.1 [M+]. MS (EI +Q1MS): 309.0 (MD , 100%), 293.2
ꢃ
ꢃ
[(MD –O), 69%], 310 [(MD +1), 26%];1H NMR
(200 MHz, CDCl3): d 8.1–7.1 (m, 12H, Ar-H), 5.17 (s, 1H,
Ar-CH(O)N), 4.63–4.55 (d, 1H, J¼12.2 Hz, Ar-CH2N),
3.94–3.88 (d, 1H, J¼11.88 Hz, Ar-CH2N); 13C NMR