Y. Hu et al. / Tetrahedron 71 (2015) 1425e1430
1429
(t, J¼5.6 Hz, 2H), 2.80 (t, J¼6.2 Hz, 1.8H), 2.00 (m, 2H); 13C NMR
(100 MHz, CDCl3)
d
148.4, 144.4, 129.3, 126.3, 124.6, 123.5, 118.3,
(100 MHz, CDCl3)
d
145.6, 138.8, 129.0, 128.5, 127.1, 126.7, 126.6,
115.8, 50.8, 27.0 (p, JCeD¼20.0 Hz), 22.5; MS (ESI): m/z 212.2
122.2, 115.8, 110.9, 54.5 (t, JCeD¼20.0 Hz), 49.8, 28.2, 27.8 (t,
[MþH]þ.
JCeD¼20.0 Hz), 22.3; MS (ESI): m/z 228.2 [MþH]þ.
4.2.22. N-(Benzyl-d2)-N-methylbenzamide (4d). Yellow oil (91%). 1H
NMR (400 MHz, CDCl3)
NMR (100 MHz, CDCl3)
4.2.13. 2-Phenylisoindoline-d4 (2n). White solid (78%). Mp
d
7.46e7.16 (m, 10H), 3.01e2.84 (m, 3H); 13
C
167.8e171.9 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.33e7.25 (m, 6H), 6.74
d
172.1,171.4,136.8,136.3,136.1,129.5,128.6,
(tt, J¼7.2, 0.1 Hz, 1H), 6.69 (dd, J¼8.7, 0.1 Hz, 2H); 13C NMR
128.3, 128.1, 127.4, 126.7, 126.1, 36.8, 32.9, 30.2, 29.5; MS (ESI): m/z
(100 MHz, CDCl3)
d 147.3, 137.9, 129.4, 127.1, 122.6, 116.1, 111.5, 53.1
228.1 [MþH]þ.
(t, JCeD¼21.0 Hz); MS (ESI): m/z 200.1 [MþH]þ.
4.2.23. (3,4-Dihydroisoquinolin-1,4-d4-2(1H)-yl)(phenyl)methanone
4.2.14. N,N0-(Pyridine-3,5-d2-2,6-diylbis(methylene-d2))bis(N-iso-
(4e). Colorless oil (87%). 1H NMR (400 MHz, CDCl3)
d
7.45e7.39 (m,
5H), 7.18e7.14 (m, 4H), 3.96 (s, 0.8H), 3.60 (s, 1.2H), 2.93 (s, 0.6H),
2.85 (s, 0.9H); 13C NMR (100 MHz, CDCl3)
170.7, 170.3, 136.0, 134.5,
propylpropan-2-amine) (2q). Brown solid (91%). Mp: 57.4e58.5 ꢀC;
1H NMR (400 MHz, CDCl3)
d
7.58 (t, J¼7.6 Hz, 1H), 7.45 (d, J¼7.6 Hz,
d
1.8H), 3.75 (s, 0.4 Hz), 3.10e3.01 (m, 4H), 1.03 (d, J¼6.4 Hz, 24H); 13
C
133.8, 132.7, 129.6, 128.5, 128.3, 126.7, 126.5, 125.7, 45.0, 40.3, 29.4,
NMR (100 MHz, CDCl3)
d
162.7, 136.5, 119.1, 51.07 (dt, JCeD¼20 Hz),
28.1; MS (ESI): m/z 240.2/241.2¼3:2 [MþH]þ.
48.8, 20.8 MS (ESI): m/z 310.3 [MþH]þ.
4.2.24. 1-(3,4-Dihydroisoquinolin-1,4-d4 -2(1H)-yl)-2,2-
4.2.15. 2,6-Bis(piperidin-1-ymmehyl-d2)pyridine-3,5-d2 (2r). Brown
oil (87%). 1H NMR (400 MHz, CDCl3)
dimethylpropan-1-one (4f). White solid (87%). Mp 58.1e60.0 ꢀC. 1H
d
7.60 (t, J¼8.4 Hz, 1H), 7.31 (t,
NMR (400 MHz, CDCl3) d 7.19e7.10 (m, 4H), 3.83 (s, 2H), 1.32 (s, 9H);
J¼7.6 Hz, 1.77H), 3.61 (d, J¼10.4, 0.17H), 2.45 (s, 8H), 1.60 (td,
J¼11.2 Hz, J¼5.6 Hz, 8H), 1.48e1.41 (m, 4H); 13C NMR (100 MHz,
13C NMR (100 MHz, CDCl3)
d 176.7, 134.3, 133.5, 128.6, 126.5, 126.3,
126.2, 43.1, 38.8, 28.3; MS (ESI): m/z 222.2 [MþH]þ.
CDCl3)
d
158.1, 136.4, 121.2, 64.2 (dt, JCeD¼19.9 Hz), 54.6, 25.8, 24.2;
MS (ESI): m/z 278.3 [MþH]þ.
4.2.25. 1-Isopropyl-4-(phenoxymethyl)benzene-d2 (6b). Colorless
oil (95%). 1H NMR (400 MHz, CDCl3)
d 7.44e7.40 (m, 2H),
4.2.16. N-(Benzyl-d2)-1-(4-methoxyphenyl)-N-(methylmethan-d2)
7.39e7.35 (m, 2H), 7.32e7.29 (m, 1H), 7.16e7.11 (m, 2H),
amine (2s). Colorless oil (92%). 1H NMR (400 MHz, CDCl3)
6.92e6.88 (m, 2H), 2.92e2.80 (m, 1H), 1.22 (d, J¼6.8 Hz, 6H); 13C
d
7.34e7.30 (m, 5H), 7.26e7.22 (m, 2H), 6.87e6.83 (m, 2H), 3.78 (s,
NMR (100 MHz, CDCl3) d 156.9, 141.3, 137.2, 128.5, 127.8, 127.5,
3H), 3.46 (s, 2H), 2.16 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
158.7,
127.2, 114.6, 69.4 (t, JCeD¼21.0 Hz), 33.3, 24.2; MS (EI): m/z 228.1
139.3, 131.4, 130.1, 129.0, 128.2, 126.9, 113.7, 61.2, 55.3, 42.1; MS
(Mþ, 16), 93.0 (100).
(ESI): m/z 244.2 [MþH]þ.
4.2.26. 9H-Xanthene-9-d2
(6c). White
solid
(73%).
Mp
4.2.17. N-(Benzyl-d2)-N-methyl-1-(pyridine-6-d1-2-yl-)(methan-d2)
101.2e102.5 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.26e7.16 (m, 4H),
amine (2t). Yellow oil (89%). 1H NMR (400 MHz, CDCl3)
d
8.54e8.52
7.06e7.02 (m, 4H); 13C NMR (100 MHz, CDCl3)
d
152.0, 128.9, 127.6,
(m, 0.85H), 7.64 (td, J¼7.7, 1.8 Hz, 1H), 7.52e7.48 (m, 1H), 7.39e7.35
(m, 2H), 7.33e7.29 (m, 2H), 7.26e7.21 (m, 1H), 7.15e7.11 (m, 1H),
3.59 (s, 0.59H), 3.56 (m, 0.51H), 2.24 (s, 3H); 13C NMR (100 MHz,
122.9, 120.5, 116.5; MS (EI): m/z 184.1 (Mþ, 76), 183.1 (90), 182.0
(100).
CDCl3)
d
159.6, 148.9, 138.9, 136.3, 128.9, 128.1, 126.9, 122.9, 121.8,
4.2.27. Diphenylmethane-d2 (6d). Colorless oil (78%). 1H NMR
62.0, 61.6 (t, JCeD¼20.0 Hz), 42.3; MS (ESI): m/z 215.2/216.2¼1:3
(400 MHz, CDCl3) d
7.28e7.10 (m, 10H); 13C NMR (100 MHz, CDCl3)
[MþH]þ.
d
141.0, 128.9, 128.4, 126.0, 41.2 (t, JCeD¼20.0 Hz); MS (EI): m/z 170.1
(Mþ, 98), 169.1 (100).
4.2.18. N-(4-tert-Butylbenzyl-d2)-N-methyl-1-(naphthalene-1-
yl)(methan-d2)amine (2u). Colorless oil (87%). 1H NMR (400 MHz,
4.2.28. 1,2,3,4-Tetrahedronaphthalene-1,4-d4 (6e). Colorless oil
CDCl3)
7.40e7.36 (m,1H), 7.34e7.26 (m, 4H), 3.57 (s,1.5H), 2.20 (s, 3H),1.30
(s, 9H); 13C NMR (100 MHz, CDCl3)
149.8, 136.3, 135.0,133.9, 132.6,
d
8.24e8.20 (m, 1H), 7.83e7.73 (m, 2H), 7.49e7.42 (m, 3H),
(83%). 1H NMR (400 MHz, CDCl3)
d 7.09e7.03 (m, 4H), 2.74 (m,
0.27H), 1.77 (s, 4H); 13C NMR (100 MHz, CDCl3)
d 137.1, 129.1, 125.4,
d
28.8 (p, JCeD¼19.0 Hz), 23.0; MS (EI): m/z 136.1 (Mþ, 96), 135.1 (46),
128.8, 128.3, 127.8, 127.3, 125.6, 125.5, 125.0, 124.9, 62.0, 42.3, 34.4,
107.1 (82), 106.1 (100).
31.4; MS (ESI): m/z 320.3/321.3¼4:1 [MþH]þ.
4.2.29. 1,3-Dimethoxyl-5-(methyl-d3)benzene-2-d1 (6f). Colorless
4.2.19. 1-Methylindoline-3-d2 (4a). Colorless oil (73%). 1H NMR
oil (82%). 1H NMR (400 MHz, CDCl3)
d 6.33 (s, 2H), 6.28 (m, 0.54H),
(400 MHz, CDCl3)
d
7.09e7.06 (m, 2H), 6.66 (t, J¼7.4 Hz,1H), 6.48 (d,
3.76 (s, 6H); 13C NMR (100 MHz, CDCl3)
d 160.7, 140.0, 107.1, 97.5,
J¼4.2 Hz, 1H), 3.26 (s, 2H), 2.74 (s, 3H); 13C NMR (100 MHz, CDCl3)
55.2, 20.9 (p, JCeD¼19.0 Hz); MS (EI): m/z 154.9 (Mþ, 100).
d
153.4, 130.1, 127.3, 124.3, 117.7, 107.2, 56.0, 36.3, 28.1 (p,
JCeD¼21.0 Hz); MS (ESI): m/z 136.1 [MþH]þ.
4.2.30. 2-(Methyl-d3)quinoline-3-d1 (6g). Brown oil (90%). 1H NMR
(400 MHz, CDCl3)
(dt, J¼1.5, 8.0 Hz, 1H), 7.50 (dt, J¼1.1, 8.0 Hz, 1H), 7.27 (d, J¼8.4 Hz,
0.63H), 2.75e2.70 (m, 0.24H); 13C NMR (100 MHz, CDCl3)
158.7,
d
8.06e8.01 (m, 2H), 7.76 (d, J¼8.0 Hz, 1H),
d 7.70
4.2.20. 1-Methyl-1,2,3,4-tetrahydroquinoline-4-d2 (4b). Brown oil
(78%). 1H NMR (400 MHz, DMSO-d6),
d
7.00e6.93 (m, 1H),
d
6.86
d
(dd, J¼7.2, 1.6 Hz, 1H), 6.54 (d, J¼8.0 Hz, 1H), 6.50 (td, J¼7.4, 1.2 Hz,
147.7, 135.8, 129.2, 128.5, 127.3, 126.3, 125.5, 121.8, 24.4 (p,
1H), 3.15 (t, J¼5.8 Hz, 2H), 2.80 (s, 3H), 1.85 (t, J¼5.6 Hz, 2H); 13C
JCeD¼20.0 Hz); MS (ESI): m/z 145.1/146.1¼1:1 (MþHþ).
NMR (100 MHz, DMSO-d6)
d 146.6, 128.4, 126.8, 122.1, 115.7, 110.7,
50.5, 38.6, 26.6 (p, JCeD¼19.0 Hz), 21.7; MS (ESI): m/z 150.1 [MþH]þ.
4.2.31. 1-(2-(Methyl-d3 )-1-enyl-1-d1 -3-d3 )naphthalene
(6h). Colorless oil (86%). 1H NMR (400 MHz, CDCl3)
d 7.99e7.97 (m,
4.2.21. 1-Phenyl-1,2,3,4-tetrahydroquinoline-4-d2 (4c). Yellow oil
1H), 7.83e7.80 (m, 1H), 7.70 (d, J¼8.0 Hz, 1H), 7.46e7.41 (m, 3H),
(90%). 1H NMR (400 MHz, CDCl3)
d
7.33 (t, J¼7.8 Hz, 2H), 7.25e7.21
7.29e7.26 (m, 1H), 6.65 (s, 0.1H), 1.97 (s, 0.3H), 1.67 (s, 0.3H); 13C
(m, 2H), 7.08 (t, J¼7.2 Hz, 1H), 7.03 (dd, J¼7.4, 1.4 Hz, 1H), 6.94e6.89
NMR (100 MHz, CDCl3)
d 136.6, 135.9, 133.6, 132.2, 128.3, 126.7,
(m, 1H), 3.62 (t, J¼5.6 Hz, 2H), 2.02 (t, J¼5.6 Hz, 2H); 13C NMR
126.6, 125.5, 125.3, 125.2, 123.0, 25.4 (t, JCeD¼19.0 Hz), 18.9 (t,