PAPER
Alkylation of Chiral Perhydro 1,3,2-Oxazabenzophosphorinane-2-oxides
823
IR (KBr): 3010, 2945, 1215, 1190, 1065, 880, 721 cm–1.
J = 6.5, 10.0, 17.0 Hz, 1 H), 7.13–7.17 (m, 2 H), 7.20–7.34 (m, 6 H),
7.58 (d, J = 7.1 Hz, 2 H).
1H NMR (CDCl3): d = 0.97 (dd, J = 7.2 Hz, JP = 17.9 Hz, 3 H), 0.98
(d, J = 6.5 Hz, 3 H), 1.06–1.23 (m, 1 H), 1.19 (s, 3 H), 1.43 (s, 3 H),
1.47–1.57 (m, 1 H), 1.63–1.85 (m, 6 H), 2.16–2.22 (m, 1 H), 2.30–
2.38 (m, 1 H), 3.11–3.20 (m, 1 H), 4.30–4.39 (m, 1 H), 4.40 (dd,
J = 17.3 Hz, JP = 12.5 Hz, 1 H), 4.47 (dd, J = 17.3 Hz, JP = 12.2 Hz,
1 H), 6.80–6.82 (m, 2 H), 7.12–7.26 (m, 3 H), 7.26–7.36 (m, 3 H),
7.50 (d, J = 7.0 Hz, 2 H).
13C NMR (CDCl3): d = 12.5, 21.6, 21.8, 26.1, 26.8 (JPC = 5.8 Hz),
30.9, 34.1, 35.8 (JPC = 129.9 Hz), 37.2, 42.5 (JPC = 7.1 Hz), 46.2,
50.9 (JPC = 4.4 Hz), 60.1, 74.0 (JPC = 7.6 Hz), 126.0, 126.9, 127.7
13C NMR (CDCl3): d = 21.7, 22.5, 25.0 (JPC = 3.2 Hz), 25.6, 30.6,
33.5, 33.7, 41.5 (JPC = 7.1 Hz), 46.3 47.7 (JPC = 126.2 Hz), 48.3
(JPC = 4.7 Hz), 59.5, 74.8 (JPC = 8.9 Hz), 116.0, 126.6, 126.9, 127.8
(2 × C), 128.0 (2 × C), 128.7 (2 × C), 129.6, 129.7, 136.2 (JPC = 16.2
Hz), 137.0, 140.0.
31P NMR (CDCl3): d = 26.24.
Anal. Calcd for C27H36NO2P: C, 74.11; H, 8.29; N, 3.20. Found: C,
74.43; H, 8.09; N, 3.31.
(2 × C), 128.1 (2 × C), 128.4 (2 × C), 128.9 (2 × C), 139.8 (JPC
=
(1¢S,2R,4aS,7R,8aR)-3-Benzyl-2-(1¢,2¢-diphenylethyl)-4,4,7-tri-
methyloctahydrobenzo[e][1,3,2]oxazaphosphinine-2-oxide
(17a)
17.3 Hz), 141.0.
31P NMR (CDCl3): d = 34.29.
White solid; mp 132–133 °C (hexane); [a]D23 +7.0 (c 0.23, CHCl3).
(1¢R,2R,4aS,7R,8aR)-3-Benzyl-4,4,7-trimethyl-2-(1¢-methylpro-
pyl)octahydrobenzo[e][1,3,2]oxazaphosphinine-2-oxide (9a)
White solid; mp 94–95 °C (hexane); [a]D23 –10.7 (c 0.57, CHCl3).
IR (KBr): 2926, 1232, 1160, 1113, 1049, 875, 824 cm–1.
1H NMR (CDCl3): d = 0.90 (t, J = 7.1 Hz, 3 H), 0.99 (d, J = 6.5 Hz,
3 H), 1.03–1.16 (m, 2 H), 1.08 (dd, J = 6.4 Hz, JP = 18.3 Hz, 3 H),
1.19 (s, 3 H), 1.20 (s, 3 H), 1.26–1.40 (m, 2 H), 1.40–1.53 (m, 1 H),
1.60–1.92 (m, 5 H), 2.13–2.19 (m, 1 H), 4.28–4.35 (m, 1 H), 4.39
(d, JP = 11.7 Hz, 2 H), 7.22–7.35 (m, 3 H), 7.43–7.46 (m, 2 H).
IR (KBr): 3020, 2926, 1232, 1194, 1164, 1028, 882, 697 cm–1.
1H NMR (CDCl3): d = 0.67–0.70 (m, 2 H), 0.81–1.17 (m, 2 H), 0.88
(s, 3 H), 0.92 (d, J = 6.5 Hz, 3 H), 0.99 (s, 3 H), 1.20–1.40 (m, 1 H),
1.43–1.63 (m, 2 H), 2.03–2.10 (m, 1 H), 2.97–3.08 (m, 1 H), 3.12–
3.22 (m, 1 H), 3.53–3.60 (m, 1 H), 4.19–4.25 (m, 1 H), 4.22 (dd,
J = 15.8 Hz, JP = 10.6 Hz, 1 H), 4.54 (dd, J = 15.8 Hz, JP = 12.8 Hz,
1 H), 6.86–6.90 (m, 2 H), 6.98–7.38 (m, 11 H), 7.57 (d, J = 7.2 Hz,
2 H).
13C NMR (CDCl3): d = 21.8, 22.5, 25.4, 25.9, 29.6, 30.8, 33.9, 41.7,
46.5, 48.9, 50.2 (JPC = 125.2 Hz), 59.8, 74.8, 125.7, 126.7, 127.1,
127.9 (2 × C), 128.2 (2 × C), 128.7 (2 × C), 128.8 (2 × C), 130.0
(2 × C), 130.1 (2 × C), 136.8, 139.8, 140.2.
13C NMR (CDCl3): d = 12.2 (JPC = 14.4 Hz), 13.6 (JPC = 4.8 Hz),
21.4, 21.8, 23.0, 26.0, 26.6 (JPC = 5.6 Hz), 30.8, 34.0, 34.9 (JPC
=
124.8 Hz), 42.4 (JPC = 7.3 Hz), 46.1, 50.7 (JPC = 4.2 Hz), 59.8, 73.7
(JPC = 8.3 Hz), 126.6, 127.4 (2 × C), 128.1 (2 × C), 140.9.
31P NMR (CDCl3): d = 35.28.
31P NMR (CDCl3): d = 26.40.
Anal. Calcd for C31H38NO2P: C, 76.36; H, 7.86; N, 2.87. Found: C,
76.19; H, 7.74; N, 3.07.
(1¢R,2R,4aS,7R,8aR)-3-Benzyl-2-(1¢,2¢-dimethylpropyl)-4,4,7-
trimethyloctahydrobenzo[e][1,3,2]oxazaphosphinine-2-oxide
(10a)
(1¢R,2R,4aS,7R,8aR)-3-Benzyl-2-(1¢,2¢-diphenylethyl)-4,4,7-tri-
methyloctahydrobenzo[e][1,3,2]oxazaphosphinine-2-oxide
(17b)
White solid; mp 88–90 °C (hexane); [a]D23 –19.2 (c 0.48, CHCl3).
IR (KBr): 3030, 2924, 1211, 1161, 1088, 868, 813 cm–1.
Colorless oil; [a]D23 –39.3 (c 0.23, CHCl3).
1H NMR (CDCl3): d = 0.84 (d, J = 6.8 Hz, 3 H), 0.92 (d, J = 6.8 Hz,
3 H), 0.96 (d, J = 6.7 Hz, 3 H), 0.99 (dd, J = 7.0 Hz, JP = 18.7 Hz, 3
H), 1.01–1.22 (m, 2 H), 1.15 (s, 3 H), 1.22 (s, 3 H), 1.31–1.48 (m, 2
H), 1.57–1.70 (m, 1 H), 1.72–1.81 (m, 3 H), 2.10–2.14 (m, 1 H),
2.17–2.34 (m, 1 H), 4.25–4.35 (m, 1 H), 4.31 (dd, J = 17.8 Hz, JP =
10.7 Hz, 1 H), 4.40 (dd, J = 17.8 Hz, JP = 12.8 Hz, 1 H), 7.18–7.32
(m, 3 H), 7.39 (d, J = 7.2 Hz, 2 H).
13C NMR (CDCl3): d = 8.8 (JPC = 4.6 Hz), 18.0, 21.0, 21.8, 22.1
(JPC = 16.9 Hz), 25.9, 26.8 (JPC = 6.3 Hz), 27.0, 30.8, 34.1, 38.0
(JPC = 128.6 Hz), 42.3 (JPC = 7.5 Hz), 46.0, 50.7 (JPC = 3.0 Hz), 59.8,
73.5 (JPC = 8.5 Hz), 126.6, 127.0 (2 × C), 128.1 (2 × C), 141.0.
IR (neat): 3028, 2952, 1235, 1166, 1028, 749, 699 cm–1.
1H NMR (CDCl3): d = 0.81 (s, 3 H), 0.85–1.15 (m, 3 H), 0.98 (d,
J = 6.5 Hz, 3 H), 1.22 (s, 3 H), 1.34–1.60 (m, 1 H), 1.63–1.77 (m, 3
H), 2.14–2.19 (m, 1 H), 2.96 (ddd, J = 3.8, 17.6 Hz, JP = 10.7 Hz, 1
H), 3.18 (ddd, J = 8.9, 17.6 Hz, JP = 17.6 Hz, 1 H), 3.51–3.60 (m, 1
H), 3.57 (dd, J = 16.8 Hz, JP = 12.0 Hz, 1 H), 3.99 (dd, J = 16.8 Hz,
JP = 9.8 Hz, 1 H), 4.23–4.33 (m, 1 H), 6.88–7.42 (m, 15 H).
13C NMR (CDCl3): d = 21.8, 22.8, 25.7, 26.2, 30.9, 34.0, 37.6 (JPC
= 2.4 Hz), 42.5 (JPC = 5.4 Hz), 46.1, 50.4, 53.6 (JPC = 122.6 Hz),
60.1, 75.7 (JPC = 7.8 Hz), 125.9, 126.7, 126.8, 127.9 (2 × C), 127.8
(2 × C), 128.1 (2 × C), 128.2 (2 × C), 128.9 (2 × C), 129.7, 129.8,
136.9 (JPC = 5.4 Hz), 140.0 (JPC = 14.6 Hz), 141.0.
31P NMR (CDCl3): d = 35.82.
Anal. Calcd for C22H36NO2P: C, 69.99; H, 9.61; N, 3.71. Found: C,
69.76; H, 9.45; N, 3.83.
31P NMR (CDCl3): d = 26.06.
(1¢S,2R,4aS,7R,8aR)-3-Benzyl-4,4,7-trimethyl-2-(1¢-phenylpro-
pyl)octahydrobenzo[e][1,3,2]oxazaphosphinine-2-oxide (18a)
White solid; mp 134–136 °C (hexane); [a]D23 –8.9 (c 1.25, CHCl3).
IR (KBr): 3027, 2925, 1230, 1162, 1117, 926, 882, 699 cm–1.
1H NMR (CDCl3): d = 0.59–0.73 (m, 2 H), 0.77 (t, J = 7.4 Hz, 3 H),
0.84 (s, 3 H), 0.88–0.94 (m, 1 H), 0.93 (d, J = 6.5 Hz, 3 H), 0.97 (s,
3 H), 0.99–1.11 (m, 1 H), 1.29–1.40 (m, 1 H), 1.45–1.52 (m, 1 H),
1.55–1.61 (m, 1 H), 1.92–2.04 (m, 1 H), 2.05–2.09 (m, 1 H), 2.18–
2.32 (m, 1 H), 2.71 (ddd, J = 3.5, 11.7, 19.3 Hz, 1 H), 4.14–4.22 (m,
1 H), 4.19 (dd, J = 16.0 Hz, JP = 11.0 Hz, 1 H), 4.54 (dd, J = 16.0
Hz, JP = 11.9 Hz, 1 H), 7.15–7.18 (m, 2 H), 7.22–7.34 (m, 6 H), 7.57
(d, J = 7.2 Hz, 2 H).
(1¢S,2R,4aS,7R,8aR)-3-Benzyl-4,4,7-trimethyl-2-(1¢-phenylbut-
3¢-enyl)octahydrobenzo[e][1,3,2]oxazaphosphinine-2-oxide
(16a)
White solid, mp 114–115 °C (hexane); [a]D23 –33.4 (c 0.67, CHCl3).
IR (KBr): 3028, 2920, 1232, 1163, 1027, 884, 701 cm–1.
1H NMR (CDCl3): d = 0.51–0.79 (m, 2 H), 0.83 (s, 3 H), 0.85–1.10
(m, 2 H), 0.92 (d, J = 6.5 Hz, 3 H), 0.98 (s, 3 H), 1.17–1.41 (m, 1
H), 1.43–1.58 (m, 2 H), 2.04–2.08 (m, 1 H), 2.67–2.80 (m, 1 H),
2.83–3.00 (m, 2 H), 4.13–4.24 (m, 1 H), 4.19 (dd, J = 15.9 Hz, JP =
10.8 Hz, 1 H), 4.54 (dd, J = 15.9 Hz, JP = 12.4 Hz, 1 H), 4.83 (dd,
J = 1.6, 10.0 Hz, 1 H), 4.93 (dd, J = 1.6, 17.0 Hz, 1 H), 5.53 (ddd,
Synthesis 2006, No. 5, 817–826 © Thieme Stuttgart · New York