4124 J . Org. Chem., Vol. 62, No. 12, 1997
Katritzky et al.
1.40-1.65 (m, 9 H), 1.20-1.30 (m, 1 H); 13C NMR δ 151.2,
138.2, 129.9, 129.0, 128.0, 127.1, 116.6, 113.1, 75.8, 69.6, 37.0,
35.9, 34.9, 25.6, 21.9, 21.6. Anal. Calcd for C20H25NO: C,
81.31; H, 8.53. Found: C, 81.21; H, 8.65.
1,1-Dicycloh exyl-2-pyr r olidin oeth an ol (2gd): white solid;
mp 51-2 °C; 1H NMR δ 2.62-2.68 (m, 4 H), 2.48 (s, 2 H), 1.67-
1.82 (m, 9 H), 1.55-1.66 (m, 5 H), 1.35-1.45 (m, 2 H), 0.95-
1.25 (m, 10 H), 0.84-0.89 (m, 1 H); 13C NMR δ 57.2, 55.8, 44.7,
27.0, 26.9, 26.8, 26.6, 24.1; HRMS (EI) calcd for C18H33NO
279.2562, found 279.2595.
1-[1-(P h en yla m in o)eth yl]-1-cycloh exa n ol (2ea ): color-
1
less oil; H NMR δ 7.10-7.18 (m, 2 H), 6.60-6.70 (m, 3 H),
3.60 (br s, 1 H), 3.38 (q, J ) 7.0 Hz, 1 H), 2.05 (br s, 1 H),
1.38-1.65 (m, 9 H), 1.16-1.30 (m, 1 H), 1.08 (d, J ) 7.0 Hz, 3
H); 13C NMR δ 148.0, 129.2, 117.3, 113.6, 73.2, 56.8, 34.7, 33.2,
25.7, 21.9, 21.6, 14.8. Anal. Calcd for C14H21NO: C, 76.67; H,
9.65; N, 6.39. Found: C, 76.22; H, 9.99; N, 6.09.
3-[(Diben zylam in o)m eth yl]-3-pen tan ol (2h b): white solid;
1
mp 54-55 °C; H NMR δ 7.26-7.39 (m, 10 H), 3.70 (s, 4 H),
2.64 (br s, 1 H), 2.57 (s, 2 H), 1.41 (q, J ) 7.2 Hz, 4 H), 0.73 (t,
J ) 7.5 Hz, 6 H); 13C NMR δ 139.2, 129.1, 128.3, 127.1, 73.7,
60.4, 59.9, 29.8, 7.7. Anal. Calcd for C20H27NO: C, 80.76; H,
9.15; N, 4.71. Found: C, 80.88; H, 9.34; N, 4.72.
Gen er a l P r oced u r e for Sm I2 Rea ction s. A solution of
the appropriate R-amino benzotriazole derivatives (2.2 mmol)
and electrophiles (2 mmol) in THF or THP (10 mL) was added
dropwise to the SmI2 solution in THF, THF-HMPA (20:1),
THP,12b or THP-HMPA (20:1) at 0 °C under argon. The
reaction was kept stirring until the deep blue (or purple) color
disappeared and then quenched with saturated aqueous
Na2CO3 solution (20 mL) at the same temperature. The
reaction mixture was separated, and the aqueous phase was
extracted with diethyl ether (2 × 20 mL). The combined
organic extracts were washed with saturated NaCl solution,
dried, and evaporated to give the crude product, which was
purified by flash column chromatography on silica gel (elu-
ent: hexanes-ethyl acetate-0.5-1% triethylamine) to afford
the pure product.
3-[(P h en ylm eth yla m in o)m eth yl]-3-p en ta n ol (2a b): col-
orless oil; 1H NMR δ 7.23 (t, J ) 8.0 Hz, 2 H), 6.90 (d, J ) 8.7
Hz, 2 H), 6.74 (t, J ) 7.2 Hz, 1 H), 3.30 (s, 2 H), 2.99 (s, 3 H),
1.76 (s, 1 H), 1.58 (q, J ) 7.4 Hz, 4 H), 0.95 (t, J ) 7.5 Hz, 6
H); 13C NMR δ 151.5, 129.0, 117.1, 112.9, 76.2, 61.2, 41.1, 29.2,
7.9. Anal. Calcd for C13H21NO: C, 75.32; H, 10.21; N, 6.76.
Found: C, 74.86; H, 10.47; N, 6.86.
N-Isopr opyl-(ph en ylm eth ylam in o)acetam ide (8): white
solid; mp 92-94 °C; 1H NMR δ 7.27 (t, J ) 7.8 Hz, 2 H), 6.84
(t, J ) 6.3 Hz, 2 H), 6.74 (d, J ) 8.4 Hz, 1 H), 6.42 (br s, 1 H),
4.13 (septet, J ) 6.6 Hz, 1 H), 3.80 (s, 3 H), 2.99 (s, 3 H), 1.11
(d, J ) 6.6 Hz, 6 H); 13C NMR δ 169.2, 149.3, 129.5, 129.2,
118.6, 113.1, 59.0, 41.0, 39.6, 22.5; MS m/z 206 (M+, 7), 120
(100). Anal. Cacld for C12H18N2O: C, 69.87; H, 8.79; N, 13.58.
Found: C, 69.88; H, 9.16; N, 13.57.
N,N′-Dip h en yl-N,N′-d im eth yl-1,2-d ip r op yleth ylen ed i-
a m in e (9). 1,2-Diiodoethane (5 mmol) was added to a suspen-
sion of samarium powder (6.5 mmol) in tetrahydropyran (THP,
50 mL) under argon at room temperature. After the mixture
was stirred for 3 h, the suspension of SmI2 in THP so formed
was cooled (-10 °C), and then N-[R-(phenylmethylamino)-
butyl]benzotriazole (1i, 2.2 mmol), 3-pentanone (2 mmol), and
HMPA (4 mL) were added successively. After the mixture had
been stirred for 4 h, saturated aqueous Na2CO3 was added,
followed by usual workup as described above. Column chro-
matography of the crude product gave 71% of 9 as a white
powder: mp 117-118 °C ; 1H NMR δ 7.23 (t, J ) 7.6Hz, 2 H),
7.14 (t, J ) 7.6 Hz, 2 H), 6.77 (d, J ) 8.2 Hz, 2 H), 6.57-6.75
(m, 4 H), 3.92-4.02 (m, 1 H), 3.81-3.91 (m, 1 H), 2.79 (s, 3
H), 2.40 (s, 3 H), 1.0-1.68 (m, 8 H), 0.90 (t, J ) 7.2 Hz, 3 H),
0.77 (t, J ) 7.2 Hz, 3 H); 13C NMR δ 151.1, 150.7, 129.2, 128.7,
115.8, 115.4, 112.2, 112.0, 60.2, 60.0, 33.8, 32.1, 31.2, 20.1, 19.8,
14.4, 14.1. Anal. Calcd for C22H32N2: C, 81.43; H, 9.94; N,
8.63. Found: C, 81.34; H, 9.91; N, 8.70.
1-(P h en ylm eth yla m in o)-3-m eth yl-2-bu ta n ol (2a f): col-
orless oil; 1H NMR δ 7.27 (t, J ) 7.8 Hz, 2 H), 6.85 (d, J ) 8.3
Hz, 2 H), 6.79 (t, J ) 7.5 Hz, 1 H), 3.67-3.74 (m, 1 H), 3.34
(dd, J ) 14.4, 3.5 Hz, 1 H), 3.25 (dd, J ) 14.4, 9.4 Hz, 1 H),
2.96 (s, 3 H), 2.27 (s, 1 H), 1.72-1.85 (m, 1 H), 1.05 (d, J ) 6.9
Hz, 3 H), 1.02 (d, J ) 6.9 Hz, 3 H); 13C NMR δ 150.7, 129.1,
117.6, 113.7, 73.4, 58.4, 39.2, 31.8, 18.7, 17.7; HRMS (EI) calcd
for C12H19NO 193.1467, found 193.1466.
Su p p or tin g In for m a tion Ava ila ble: 1H and 13C NMR and
HRMS spectra for products 2a a ,a b,a e,a f,cc,ea ,gd (16 pages).
This material is contained in libraries on microfiche, im-
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1-(Dip h en yla m in o)-2,3-d im eth ylbu ta n -2-ol (2cc): color-
1
less oil; H NMR δ 7.29-7.24 (m, 4 H), 7.06 (d, J ) 7.9 Hz, 4
H), 6.98 (t, J ) 7.4 Hz, 2 H), 3.89 (s, 2 H), 1.92 (s, 1 H), 1.81
(septet, J ) 6.9 Hz, 1 H), 1.07 (s, 3 H), 0.97 (d, J ) 6.9 Hz, 3
H), 0.86 (d, J ) 6.9 Hz, 3 H); 13C NMR δ 150.3, 129.4, 121.9,
121.8, 76.4, 61.4, 36.3, 21.8, 17.7, 17.0; MS m/z 269 (M+, 6),
251 (6), 182 (100), 169 (99); HRMS (EI) calcd for C18H23NO
270.1858, found 270.1792.
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