L. L. Schafer et al.
talyst 1 (10 mg, 0.0133) were used in the general procedure described
above. Subsequent reduction with LiAlH4 (15 mg, 0.40 mmol) gave the
desired product (44 mg, 79% yield). 1H NMR ([D3]chloroform,
173.0 ppm; MS (EI): m/z 215 [M]+, 158 [MÀtBu]+; IR (NaCl/neat): 3305
(vw, NH), 1730 (s, CO), 712 cmÀ1 (m).
tert-Butyl-5-(N-tert-butyl)aminopentanoate:
Alkyne
11
(41 mg,
300 MHz): d=1.05 (9H, s; C(CH3)3), 2.67–2.80 (4H, m; PhCH2CH2NH),
A
0.27 mmol), tert-butylamine (39 mg, 0.53 mmol), and precatalyst
1
À
3.76 (3H, s; OCH3), 6.82 (2H, d, J=8.6 Hz; Ar H), 7.10 ppm (2H, d, J=
(10 mg, 0.0133) were used in the general procedure described above. Sub-
sequent reduction with NaBH4 (15 mg, 0.40 mmol) gave the desired prod-
uct (45 mg, 74% yield). 1H NMR ([D3]chloroform, 300 MHz): d=1.07
(9H, s; CH3 3), 1.41 (9H, s; CH3 3), 1.50–1.64 (4H, m;
NHCH2CH2CH2CH2CO), 1.76 (1H, brs; NH), 2.20 (2H, t, J=7.1 Hz;
CH2CO), 2.52 ppm (2H, t, J=7.2 Hz; NHCH2); 13C NMR
([D3]chloroform, 75 MHz): 23.0, 28.1, 28.9, 30.37, 35.37, 42.1, 50.4, 80.1,
173.1 ppm; MS (EI): m/z 229 [M]+, 214 [MÀMe]+; IR (NaCl/neat): 3423
(vw, NH), 1735 (s, CO), 750 cmÀ1 (m); HRMS m/z: calcd for C13H27NO2:
229.20418 [M]+; found: 229.20412.
5-Oxopentylbenzoate:[51] Alkyne 12 (37 mg, 0.27 mmol), isopropylamine
(32 mg, 0.27 mmol), and precatalyst 1 (10 mg, 0.0133) were used in the
general procedure described above. Subsequent hydrolysis gave the de-
sired product (48 mg, 86% yield). With alkyne 12 (37 mg, 0.27 mmol)
and tert-butylamine (39 mg, 0.53 mmol), the product was obtained
(39 mg, 70% yield). 1H NMR ([D3]chloroform, 300 MHz): d=1.77–1.81
(4H, m; CH2 2), 2.48–2.53 (2H, m; CH2CHO), 4.31 (3H, t, J=6.0 Hz;
8.6 Hz; Ar H); 13C NMR ([D3]chloroform, 75 MHz): d=29.0, 36.2, 44.2,
À
50.2, 55.2, 113.8, 129.5, 132.2, 158.0 ppm; MS (EI): m/z: 207 [M]+, 206
[MÀH]+, 192 [MÀCH3]+; IR (NaCl/neat): 3414 (vw; NH), 3030 (w), 1514
(s), 821 cmÀ1 (w); HRMS m/z: calcd for C13H21NO: 207.16231 [M]+;
found: 207.16241.
N-(Benzyl)-[2-(4’-chloro)phenyl]ethylamine:
4’-Chlorophenylacetylene
(37 mg, 0.27 mmol), benzylamine (29 mg, 0.27 mmol), and precatalyst 1
(10 mg, 0.0133) were used in the general procedure described above. Sub-
sequent reduction with LiAlH4 (15 mg, 0.40 mmol) gave the desired
product (62 mg, 93% yield). 1H NMR ([D3]chloroform, 300 MHz): d=
1.78 (1H, brs; NH), 2.77–2.91 (4H, m; PhCH2CH2NH), 3.80 (2H, s;
À
À
NHCH2Ph), 7.13 (2H, d, J=8.4 Hz; Ar H), 7.23–7.35 ppm (7H, m; Ar
H); 13C NMR ([D3]chloroform, 75 MHz): d=35.7, 50.3, 53.8, 127.0, 128.1,
128.4, 128.5, 130.0, 131.9, 138.5, 140.1 ppm; MS(EI): m/z: 245 [M]+, 244
[MÀH]+, 91 (PhCH2+); IR (NaCl/neat): 3383 (vw; NH), 1493 (s), 1359
(m), 713 cmÀ1 (m); HRMS m/z: calcd for C15H16N35Cl: 245.09713 [M]+;
found: 245.09699.
À
À
CH2O), 7.39–7.50 (3H, m; Ar H), 7.99–8.02 (2H, m; Ar H), 9.77 ppm
(1H, t, J=1.3 Hz; CHO); 13C NMR ([D3]chloroform, 75 MHz): 18.6,
28.1, 43.3, 64.3, 128.3, 129.5, 130.2, 132.9, 166.5, 201.8 ppm; MS (EI): m/z:
207 [M]+, 105 (C6H5CO+); IR (NaCl/neat): 2939 (w), 1716 (s, CO), 1276
(s), 675 cmÀ1 (m).
N-Isopropyl-[2-(4’-chloro)phenyl]ethylamine: 4’-Chlorophenylacetylene
(37 mg, 0.27 mmol), isopropylamine (32 mg, 0.53 mmol), and precatalyst
1 (10 mg, 0.0133) were used in the general procedure described above.
Subsequent reduction with LiAlH4 (15 mg, 0.40 mmol) gave the desired
product (36 mg, 68% yield). 1H NMR ([D3]chloroform, 300 MHz): d=
N-(3-Isopropylamino)propylbenzamide: Alkyne 13 (43 mg, 0.27 mmol),
isopropylamine (31 mg, 0.53 mmol), and precatalyst 1 (10 mg, 0.0133)
were used in the general procedure described above. Subsequent reduc-
tion with NaBH4 (12 mg, 0.42 mmol) gave the desired product (45 mg,
77% yield). 1H NMR ([D3]chloroform, 300 MHz): d=1.05 (6H, d; J=
6.2 Hz; CH3 2), 1.69–1.74 (3H, m; CH2, NH), 2.74–2.80 (3H, m; CH2,
À
1.03 (6H, d, J=6.3 Hz; CH(CH3)2), 1.40 (1H, brs; NH), 2.75–2.84 (5H,
T
À
m; PhCH2CH2NH, CH(CH3)2), 7.13 (2H, d, J=8.3 Hz; Ar H), 7.25 ppm
N
À
35.9, 48.6, 128.5, 130.0, 131.9, 138.6 ppm; MS (EI): m/z: 197 [M]+, 196
[M H] , 182 [MÀCH3] ; IR (NaCl/neat): 3425 (vw, NH), 1643 (m),
623 cmÀ1 (m); HRMS m/z: calcd for C11H16N35Cl: 197.09713 [M]+; found:
197.09671.
+
+
À
CH(CH3)2), 3.51–3.54 (2H, m; CH2NHCO), 7.37–7.44 (3H, m; Ar H),
G
7.77–7.80 (2H, m; Ar H), 8.60 ppm (1H, brs; NH); 13C NMR
([D3]chloroform, 75 MHz): 22.9, 28.6, 40.4, 46.5, 48.9, 126.9, 128.3, 131.1,
134.8, 167.1; MS (EI): m/z: 209 [M+H]+, 193 [MÀMe]+; IR (NaCl/neat):
3421 (vw, NH), 1635 (s, CO), 713 cmÀ1 (m).
À
N-tert-Butyl-[2-(4’-chloro)phenyl]ethylamine: 4’-Chlorophenylacetylene
(37 mg, 0.27 mmol), tert-butylamine (39 mg, 0.53 mmol), and precatalyst
1 (10 mg, 0.0133) were used in the general procedure described above.
Subsequent reduction with LiAlH4 (15 mg, 0.40 mmol) gave the desired
product (52 mg, 91% yield). 1H NMR ([D3]chloroform, 300 MHz): d=
N-(3-tert-Butylamino)propylbenzamide: Alkyne 13 (43 mg, 0.27 mmol),
tert-butylamine (39 mg, 0.53 mmol), and precatalyst 1 (10 mg, 0.0133)
were used in the general procedure described above. Subsequent reduc-
tion with NaBH4 (12 mg, 0.32 mmol) gave the desired product (50 mg,
80% yield). 1H NMR ([D3]chloroform, 300 MHz): d=1.08 (3H, s; CH3
3), 1.57 (1H, brs; NH), 1.67–1.75 (2H, m; CH2), 2.76 (2H, t, J=5.5 Hz;
1.07 (9H, s; C(CH3)3), 2.71–2.82 (4H, m; PhCH2CH2NH), 7.14 (2H, d,
U
J=8.3 Hz; Ar H), 7.25 ppm (2H, d, J=8.3 Hz; Ar H); 13C NMR
([D3]chloroform, 75 MHz): d=28.9, 36.5, 43.9, 50.4, 128.5, 130.0, 131.9,
138.7 ppm; MS (EI): m/z 211 [M]+, 210 [MÀH]+, 196 [MÀCH3]+; IR
(NaCl/neat): 3425 (vw, NH), 2964 (m), 1493 (m), 810 cmÀ1 (m); HRMS
m/z: calcd for C12H18N35Cl: 211.11278 [M]+; found: 211.11394.
À
À
À
CH2), 3.51–3.56 (2H, m; CH2), 7.34–7.44 (3H, m; Ar H), 7.78–7.80 (2H,
m; Ar H), 8.61 ppm (1H, brs; NH); 13C NMR ([D3]chloroform,
À
5-Oxopentyl-2’,2’-dimethylpropanoate:[50] Alkyne 10 (45 mg, 0.27 mmol),
benzylamine (29 mg, 0.27 mmol), and precatalyst 1 (10 mg, 0.0133) were
used in the general procedure described above. Subsequent hydrolysis
gave the desired product (40 mg, 80% yield). With alkyne 10 (45 mg,
0.27 mmol) and isopropylamine (31 mg, 0.53 mmol), the product was ob-
tained (45 mg, 90% yield). With alkyne 10 (45 mg, 0.27 mmol) and tert-
butylamine (39 mg, 0.53 mmol), the product was obtained (48 mg, 95%
75 MHz): d=28.8, 40.8, 42.0, 50.6, 126.9, 128.3, 131.0, 134.8, 167.0 ppm
(quaternary carbon atom not observed); MS (EI): m/z: 235 [M+H]+, 219
[MÀMe]+; IR (NaCl/neat): 3283 (w, NH), 1637 (s, CO), 707 cmÀ1 (m).
Methyl-4-[2-(isopropylamino)ethyl]benzoate:
Alkyne
14
(43 mg,
0.27 mmol), isopropylamine (31 mg, 0.53 mmol), and precatalyst
1
(10 mg, 0.0133) were used in the general procedure described above. Sub-
sequent reduction with NaBH4 (12 mg, 0.42 mmol) gave the desired prod-
uct (42 mg, 70% yield). 1H NMR ([D3]chloroform, 300 MHz): d=1.03
1
yield). H NMR ([D3]chloroform, 300 MHz): d=1.77–1.81 (4H, m; CH2
2), 2.48–2.53 (2H, m; CH2CHO), 4.31 (3H, t, J=6.0 Hz; CH2O), 7.39–
(6H, d, J=6.2 Hz; CH
A
À
À
À
7.50 (3H, m; Ar H), 7.99–8.02 (2H, m; Ar H), 9.77 ppm (1H, t, J=
1.3 Hz; CHO); 13C NMR ([D3]chloroform, 75 MHz): 18.6, 28.1, 43.3, 64.3,
128.3, 129.5, 130.2, 132.9, 166.5, 201.8 ppm; MS (EI): m/z: 207 [M]+, 105
(C6H5CO+); IR (NaCl/neat): 2939 (w), 1716 (s, CO), 1276 (s), 675 cmÀ1
(m).
CH2 2, CH(CH3)2), 3.88 (3H, s; OCH3), 7.25 (2H, d, J=6.3 Hz; Ar H),
AHCTREUNG
7.94 ppm (2H, d, J=6.3 Hz; Ar H); 13C NMR ([D3]chloroform,
75 MHz): d=22.8, 36.5, 48.3, 48.6, 60.8, 128.6, 128.7, 129.8, 145.4,
166.6 ppm; MS (EI): m/z: 221 [M]+, 220 [MÀH]+, 206 [MÀCH3]+; IR
(NaCl/neat): 3429 (vw, NH), 1682 (s, CO), 1311 (m), 744 cmÀ1 (w);
HRMS: m/z: calcd for C13H19NO2: 221.14158 [M]+; found: 221.14083.
À
tert-Butyl-5-(N-isopropyl)aminopentanoate:
Alkyne
11
(41 mg,
0.27 mmol), isopropylamine (32 mg, 0.53 mmol), and precatalyst
1
Methyl-4-[2-(tert-butylamino)ethyl]benzoate:
Alkyne
14
(43 mg,
(10 mg, 0.0133) were used in the general procedure described above. Sub-
sequent reduction with NaBH4 (15 mg, 0.40 mmol) gave the desired prod-
uct (48 mg, 85% yield). 1H NMR ([D3]chloroform, 300 MHz): d=1.02
(6H, d, J=6.2 Hz; CH3 2), 1.41 (9H, s; CH3 3), 1.44–1.62 (4H, m;
NHCH2CH2CH2CH2CO), 2.20 (2H, t, J=6.9 Hz; CH2CO), 2.57 (2H, t,
0.27 mmol), tert-butylamine (39 mg, 0.53 mmol), and precatalyst
1
(10 mg, 0.0133) were used in the general procedure described above. Sub-
sequent reduction with NaBH4 (12 mg, 0.32 mmol) gave the desired prod-
uct (58 mg, 91% yield). 1H NMR ([D3]chloroform, 300 MHz): d=1.04
(9H, s; C(CH3)3), 2.80 (4H, brs; CH2 2), 3.87 (3H, s; OCH3), 7.25 (2H,
A
J=7.0 Hz; NHCH2), 2.76 ppm (1H, m; CH
([D3]chloroform, 75 MHz): 22.9, 28.1, 29.8, 35.4, 47.1, 48.7, 80.1,
(CH3)2); 13C NMR
d, J=6.3 Hz; Ar H), 7.92 (2H, d, J=6.3 Hz; Ar H); 13C NMR
([D3]chloroform, 75 MHz): d=28.9, 37.2, 43.6, 50.3, 52.0, 128.1, 128.7,
À
À
2020
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 2012 – 2022