Page 9 of 14
The Journal of Organic Chemistry
(d, JP-C=9.35 Hz), 130.8 (d, JP-C=2.53 Hz), 130.5 (d, JF-C=4.61 Hz), 129.1 (d, JF-C=8.19 Hz), 128.0 (d, JP-C=9.53 Hz), 127.6 (d, JC-F= 6.38
Hz), 127.4 (d, JC-F=6.33 Hz), 124.2 (d, JC-F=3.49 Hz), 41.1 (m), 30.94 (d, JP-C=40 Hz), 24.63 (d, JP-C=2.85 Hz); 11B NMR (128MHz CDCl3):
δ -46,26 ; IR (ATR) 3337, 2960, 2941, 9865, 9835, 2383, 1602, 1491, 1462, 1423, 1303, 1239, 1160, 1109, 1049, 999, 924, 856, 811, 760,
735, 694, 641, 618, 600, 564; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C17H24BFNPNa 326.1619; Found 326.1622; Rf=0.4 (9:1
Petroleum ether/AcOEt) HPLC separation (Lux-Cellulose-2, heptane / isopropanol (95:5), 1 mL / min, 254 nm), r.t. first eluted 6.86 min
(major), r.t. second eluted 9.18 min (minor), e.r. = 94:6
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(RP)-N-o-methoxybenzyl-1-phenyl-1-(tert-butyl)phosphinamine borane) (2c, MW=315 g/mol) was obtained according to the general
1
procedure from o-methoxybenzylamine as a white solid in 63 % yield. M.p. = 90.3-90.4 °C; H NMR (400MHz CDCl3): δ 7.64 (m, 2H),
7.40 (m, 3H), 7.25 (m, 2H), 6.86 (m, 2H), 4.24 (dd, ABX system, 1H), 4.16 (dd, ABX system, 1H), 3.88 (s, 3H), 2.5 (bs; 1H, NH), 1.08 (d,
J= 14.08 Hz, 9H), 0.91 – 0.5 (t, 3H, BH3); 31P{1H} NMR (162 MHz CDCl3): δ 70.30 (m, 1P) ; 13C{1H} NMR (101 MHz CDCl3): δ 157.6
(s), 131.9 (d, JP-C=9.35 Hz), 130.8 (d, JP-C=2.53 Hz), 130.5 (d, JP-C=2.53 Hz), 129.8 (s), 128.7 (s), 127.9 (d, JC-P=9.43 Hz), 120.7 (s),110.3
(s), 55.28 (s), 43.2 (d, JP-C=2 Hz), 30.7 (d, JP-C=45 Hz), 24.7 (d, JP-C=2.78 Hz) 11B NMR (128MHz CDCl3): δ -42,22 ; IR (ATR) 3351, 3328,
3060, 2966, 2913, 1867, 2343, 2265, 1585, 1485, 1433, 1421, 1363, 1330, 1293, 1177, 1076, 1014, 998, 862, 848, 814, 774, 755, 695, 645,
573, 519 ; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C18H27BNOPNa 338.1819; Found 338.1816; Rf=0.3 (9:1 Petroleum ether/AcOEt)
HPLC separation (Chiralcel OD-3, heptane / isopropanol (95:5), 1 mL / min, 220 nm), r.t. first eluted 6.061 min (minor), r.t. second eluted
7.446 min (major), e.r. = 7 : 93
(RP)-N-o-chlorobenzyl-1-phenyl-1-(tert-butyl)phosphinamine borane) (2d, MW=319 g/mol) was obtained according to the general procedure
from o-chlorobenzylamine as a white solid in 72 % yield. M.p. = 81.3-90.6 °C 1H NMR (400MHz CDCl3): δ 7.61 (m, 2H), 7.40 (m, 5H),
7.17 (m, 2H), 4.37 (dd, ABX system, 1H), 4.26 (dd, ABX system, 1H), 2.59 (bs; 1H, NH), 1.09 (d, J= 14.12 Hz, 9H), 0.91 – 0.5 (t, 3H, BH3);
31P{1H} NMR (162 MHz CDCl3): δ 71.15 (m, 1P) ; 13C{1H} NMR (101 MHz CDCl3) : δ 137.9 (d, JP-H=5.82 Hz), 133.5 (s), 131.7 (d, JP-
C=9.35 Hz), 130.7 (s), 130.7 (d, JP-C=2.53 Hz), 130.5 (d, JP-C=2.53 Hz), 129.4 (s), 128.8 (s), 128.0 (d, JC-P=9.51 Hz), 127.1 (s), 45.0 (d, JP-
C=2,49 Hz), 30.9 (d, JP-C=45 Hz), 24.6 (d, JP-C=2.84 Hz) 11B NMR (128MHz CDCl3): δ -42,3 ; IR (ATR) 3384, 3328, 3061, 2963, 2930,
2902, 1384, 2340, 1588, 1572, 1434, 1405, 1363, 1328, 1261, 1244, 1126, 1091, 1067, 1047, 1014, 1000, 940, 912, 891, 867, 815, 754, 739,
701, 612, 599; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C17H24BClNPNa 342.1323; Found 342.1321; Rf=0.4 (9:1 Petroleum
ether/AcOEt) HPLC separation (Chiralpak AS-H, heptane / isopropanol (95:5), 1 mL / min, 220 nm), r.t. first eluted 4.52 min (major), r.t.
second eluted 5.32 min (minor), e.r. = 89 : 11
(RP)-N-m-methoxybenzyl-1-phenyl-1-(tert-butyl)phosphinamine borane) (2e, MW=315 g/mol) was obtained according to the general
procedure from m-methoxybenzylamine as a white solid in 76 % yield. M.p. = 63.9-64.0 °C; 1H NMR (400MHz CDCl3): δ 7.68 (m, 2H),
7.45 (m, 3H), 7.24 (m, 1H), 6.92 (m, 2H), 6.82 (m, 1H) 4.29 (dd, ABX system, 1H), 4.09 (dd, ABX system, 1H), 3.76 (s, 3H), 2.02 (bs; 1H,
NH), 1.08 (d, J= 14.08 Hz, 9H), 0.91 – 0.5 (t, 3H, BH3); 31P{1H} NMR (162 MHz CDCl3): δ 71.12 (m, 1P) ; 13C{1H} NMR (101 MHz
CDCl3): δ 157.6 (s), 142.3 (d, JP-H=7.41 Hz), 131.9 (d, JP-C=9.35 Hz), 130.8 (d, JP-C=2.53 Hz), 129.8 (s), 129.6 (s), 128.12 (d, JC-P=9.50 Hz),
120.3 (s),113.2 (d, JP-H=12.62 Hz), 55.16 (s), 47.7 (d, JP-C=2 Hz), 30.7 (d, JP-C=45.3 Hz), 24.7 (d, JP-C=2.82 Hz) 11B NMR (128MHz CDCl3):
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